TW202317583A - Heterocyclic compound, organic light emitting device, and composition for organic material layer of organic light emitting device - Google Patents

Abstract

The present specification relates to a heterocyclic compound, an organic light emitting device, and a composition for an organic material layer of an organic light emitting device.

Description

Heterocyclic compound, organic light-emitting element and composition of organic material layer of organic light-emitting element

This specification is about a heterocyclic compound, an organic light-emitting element and a composition of an organic material layer used in the organic light-emitting element.

This application claims priority and benefit from Korean Patent Application No. 10-2021-0082538 filed with the Korean Intellectual Property Office on June 24, 2021, the entire contents of which are incorporated herein by reference middle.

The electroluminescent element is a self-emissive display element, and has the advantages of wide viewing angle, excellent contrast ratio and fast response rate.

An organic light emitting element has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting element having the structure, electrons and holes injected from both electrodes combine with each other in the organic thin film to form a pair, and then emit light while being turned off. The organic thin film may consist of a single layer or multiple layers, as desired.

The material used for the organic thin film may have a light emitting function if necessary. For example, regarding the material used for the organic thin film, it is also possible to use a compound which itself can constitute a light-emitting layer or a compound which can serve as a host or a dopant for a host-dopant type light-emitting layer. In addition, with regard to materials for organic thin films, it is also possible to use compounds that can exert effects such as hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection.

In order to improve the performance, service life or efficiency of organic light-emitting devices, it is necessary to continuously develop materials for organic thin films.

[Prior Art Literature] [Patent Document] (Patent Document 1) US Patent No. 4,356,429

[technical problem] This specification is devoted to a heterocyclic compound, an organic light-emitting element, and a composition of an organic material layer for an organic light-emitting element. [Technical solution]

。 In an exemplary embodiment of the present specification, a heterocyclic compound of the following chemical formula 1 is provided: [chemical formula 1]

.

的氘含量大於0%。 In Chemical Formula 1, X is O; S; or CRR', L is a direct bond; or a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, l is an integer of 1 to 3, and When l is 2 or greater than 2, L' are the same or different from each other, A is an aromatic ring having 6 to 60 carbon atoms, which is unsubstituted or substituted with deuterium; or a heterocyclic ring having 2 to 60 carbon atoms Ring, which is unsubstituted or substituted with deuterium, R, R', Ar1 and Ar2 are each independently hydrogen; deuterium; halo; cyano; substituted or unsubstituted alkane having 1 to 60 carbon atoms substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; substituted or unsubstituted heterocycloalkyl having 2 to 60 carbon atoms; having 6 to 60 carbons Atomic substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms, H is hydrogen and D is deuterium, d is an integer from 0 to 6; and chemical formula 1

The deuterium content is greater than 0%.

In another exemplary embodiment of the present specification, an organic light-emitting element is provided, which includes: a first electrode; a second electrode disposed facing the first electrode; and an organic material layer having a One or more layers between the electrodes, wherein one or more of the organic material layers comprise heterocyclic compounds.

In yet another exemplary embodiment of the present specification, a composition for an organic material layer of an organic light-emitting device is provided, which includes a heterocyclic compound.

的位置處必須包含氘而用作有機發光元件的發光層大材料時，分子的穩定性藉由減少振動頻率的變化而增強且熱穩定性由於較高的單鍵解離能量而增加，使得在驅動電壓、發光效率及使用壽命方面提供極佳的效能。 [Advantageous Effects] When used in an organic light-emitting element, the heterocyclic compound described in this specification can reduce the driving voltage of the element, improve light efficiency, and improve the lifetime characteristics of the element. Specifically, when the heterocyclic compound of chemical formula 1 has a core structure

When deuterium must be contained at the position of the organic light-emitting element and used as a large material for the light-emitting layer of the organic light-emitting element, the stability of the molecule is enhanced by reducing the change in vibration frequency and the thermal stability is increased due to the higher single-bond dissociation energy. It provides excellent performance in terms of voltage, luminous efficiency and service life.

Hereinafter, the specification will be described in more detail.

In this specification, when a component "includes" a constituent member, unless specifically described otherwise, this does not mean excluding another constituent member, but means that another constituent member may be further included.

意謂組成構件所鍵結的位置。 In this specification, the chemical formula of

Means the position where the constituent members are bonded.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the substituted position is not limited as long as the position is a hydrogen atom substituted position, that is, the substituent can be replaced by The position of substitution, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

In this specification, "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halo; cyano; C1 to C60 Alkyl; C2 to C60 alkenyl; C2 to C60 alkynyl; C3 to C60 cycloalkyl; C2 to C60 heterocycloalkyl; C6 to C60 aryl; C2 to C60 heteroaryl; silyl; phosphine oxide; and an amine group, or a substituent to which two or more of the substituents are bonded.

In the present specification, "when no substituent is indicated in the chemical formula or the structure of the compound" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, "when no substituent is indicated in the chemical formula or the structure of the compound" may mean that all positions accessible to the substituent are hydrogen; or deuterium. In other words, deuterium is an isotope of hydrogen, and some hydrogen atoms may be deuterium as an isotope, and in this case, the content of deuterium may be 0% to 100%.

In an exemplary embodiment of the present application, in "the case where no substituent is indicated in the chemical formula or the structure of the compound", when the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents are Deuterium is not expressly excluded, such as hydrogen, which can be mixed and used in compounds.

In an exemplary embodiment of the present application, deuterium is one of the isotopes of hydrogen, is an element having a deuteron formed by a proton and a neutron as an atomic nucleus, and can be expressed as hydrogen-2, and the symbol of the element is also It can be written as D or 2H.

In an exemplary embodiment of the present application, isotope means atoms with the same atomic number (Z) but different mass numbers (A), and isotopes can be interpreted as elements with the same number of protons but different numbers of neutrons .

In an exemplary embodiment of the present application, when the total number of substituents of the base compound is defined as T1 and the number of specific substituents among these substituents is defined as T2, the content T% of the specific substituent can be defined as T2/T1×100 = T%.

表示的苯基中具有20%的氘含量可表示為苯基可具有的取代基的總數目為5（公式中的T1），且所述取代基中氘的數目為1（公式中的T2）時的20%。換言之，苯基中具有20%的氘含量可由以下結構式表示。

In other words, in one example, after the

A deuterium content of 20% in the indicated phenyl group can be expressed as the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and the number of deuterium in said substituents is 1 (T2 in the formula) 20% of the time. In other words, a phenyl group having a deuterium content of 20% can be represented by the following structural formula.

In addition, in an exemplary embodiment of the present application, the "phenyl group having a deuterium content of 0%" may mean a phenyl group not containing deuterium atoms, that is, a phenyl group having five hydrogen atoms.

In this specification, halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methylpentyl Base-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl , n-octyl, tertiary octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propane radical, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl Base, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylethenyl-1-yl, 2-phenylethenyl-1-yl, 2, 2-Diphenylethenyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)ethenyl-1-yl, 2,2-bis(diphenyl-1-yl)ethenyl -1-yl, stilbenyl (stilbenyl), styryl and the like, but not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

In this specification, an alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1-20. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy, secondary butoxy, n-pentoxy, neo Pentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy group, p-methylbenzyloxy group and the like, but not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a cycloalkyl group is directly linked to or fused to another cyclic group. Here, the other cyclic group may also be a cycloalkyl group, but also another cyclic group such as heterocycloalkyl, aryl, heteroaryl and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclopentyl, Hexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but not limited thereto.

In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a heteroatom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a heterocycloalkyl group is directly bonded to or fused to another cyclic group. Here, the other cyclic group may also be a heterocycloalkyl group, but also another cyclic group such as cycloalkyl, aryl, heteroaryl and the like. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which an aryl group is directly linked to or fused to another cyclic group. Here, the other cyclic group may also be an aryl group, but also another cyclic group such as cycloalkyl, heterocycloalkyl, heteroaryl and the like. Aryl groups include spirocyclic groups. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of aryl groups include phenyl, biphenyl, terphenyl, naphthyl, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fennel Anthracenyl (fluoranthenyl group), bis-triphenylene, propylene-naphthyl (phenalenyl group), pyrenyl (pyrenyl group), fused tetraphenyl, condensed pentaphenyl, fluorenyl, indenyl (indenyl group), acenaphthyl (acenaphthylenyl group), benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, condensed ring groups thereof, and the like, but not limited thereto.

In this specification, the terphenyl group can be selected from the following structures.

In this specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

、

、

、

、

、

以及類似基團，但不限於此。 When the fluorenyl group is substituted, the substituent can be

,

,

,

,

,

and similar groups, but not limited thereto.

In the present specification, the heteroaryl group contains S, O, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a heteroaryl group is directly bonded to or fused to another cyclic group. Here, the further cyclic group may also be a heteroaryl group, but also another cyclic group such as cycloalkyl, heterocycloalkyl, aryl and the like. The number of carbon atoms of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazole Base, furanyl, oxadiazolyl, thiadiazolyl, bithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxacyl (dioxynyl group), triazinyl, tetrazinyl, quinolinyl, isoquinolyl, quinazolinyl, isoquinazolinyl, quinozolilyl group, naphthyridinyl, acridinyl, phenanthryl, imidazopyridyl, naphthyl, triacindyl, indolyl, indolazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothiophene, benzofuran , dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenhydrazinyl, dibenzosilole group, spiro two (dibenzo silole), dihydrophenanthrazinyl, phenanthoxazinyl, phenanthridyl group, imidazopyridyl, thienyl, indole[2,3-a]carbazolyl, indole[2,3 -b]carbazolyl, indolinyl, 10,11-dihydro-dibenzo[b,f]azepine, 9,10-dihydroacridinyl, phenanthazinyl, morphanthiazinyl, Hazinyl, naphthindinyl, phenanthrinyl, benzo[c][1,2,5]thiadiazolyl, 2,3-dihydrobenzo[b]thiophene, 2,3-dihydrobenzene Furan, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl, pyrido[1,2- b] Indazolyl, pyrido[1,2-a]imidazo[1,2-e]indolinyl, 5,11-dihydroindeno[1,2-b]carbazolyl and the like or, but not limited to.

（三甲基矽基）、

（三乙基矽基）、

（三級丁基二甲基矽基）、

（乙烯基二甲基矽基）、

（丙基二甲基矽基）、

（三苯基矽基）、

（二苯基矽基）、

（苯基矽基）以及類似基團，但不限於此。 In this specification, the silicon group contains Si and is a substituent directly connected to a Si atom as a free radical, and is represented by -Si(R101)(R102)(R103), and R101 to R103 are the same or different from each other, and can be independently is a substituent consisting of at least one of hydrogen; deuterium; halo; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl. Specific examples of silicon bases include

(trimethylsilyl),

(triethylsilyl),

(tertiary butyldimethylsilyl),

(vinyldimethylsilyl),

(Propyldimethylsilyl),

(triphenylsilyl),

(diphenylsilyl),

(phenylsilyl) and similar groups, but not limited thereto.

In this specification, the phosphine oxide group is represented by -P(=O)(R104)(R105), and R104 and R105 are the same or different from each other and may each independently be a substituent composed of at least one of the following: hydrogen , deuterium, halo, alkyl, alkenyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl. In particular, the phosphine oxide groups may be substituted with alkyl or aryl groups, and the examples described above may apply to both alkyl and aryl groups. Specific examples of the phosphine oxide group include dimethylphosphine oxide, diphenylphosphine oxide, dinaphthylphosphine oxide, and the like, but are not limited thereto.

In this specification, the amine group is represented by -N(R106)(R107), and R106 and R107 are the same or different from each other, and each independently is a substituent composed of at least one of the following: hydrogen, deuterium, halo , alkyl, alkenyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl. The amine group may be selected from the group consisting of: -NH ₂ ; monoalkylamine; monoarylamine; monoheteroarylamine; dialkylamine; diarylamine; An alkylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 30. Specific examples of amine groups include methylamino, dimethylamino, ethylamino, diethylamino, anilino, naphthylamino, benzidine, dibenzidine, anthracene, 9-methyl-anthracene Amine, diphenylamino, phenylnaphthylamino, xylanilinyl, phenyltoluidine, triphenylamine, biphenylnaphthylamino, phenylbenzidine, biphenylfluorenylamino, phenyltriphenylene Amylamine, biphenyltriphenylamine, and the like, but not limited thereto.

In this specification, the above-described examples of the aryl group can be applied to the arylylene group other than the divalent arylylene group.

In this specification, the above-described examples of the heteroaryl group can be applied to the heteroarylylene group other than the divalent heteroarylylene group.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Chemical Formula 1.

In an exemplary embodiment of the present specification, A is an aromatic ring having 6 to 30 carbon atoms, which is unsubstituted or substituted with deuterium; or a heterocyclic ring having 2 to 30 carbon atoms, which is not substituted or substituted with deuterium.

In an exemplary embodiment of the present specification, A is an aromatic ring having 6 to 15 carbon atoms, which is unsubstituted or substituted with deuterium; or a heterocyclic ring having 2 to 15 carbon atoms, which is not substituted or substituted with deuterium.

In an exemplary embodiment of the present specification, A is an aromatic ring having 6 to 15 carbon atoms, which is unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, A is an unsubstituted or deuterium-substituted benzene ring.

In an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 1-1. [chemical formula 1-1]

In Chemical Formula 1-1, H1 to H4 are each independently hydrogen; or deuterium, and the definitions of other substituents are the same as those in Chemical Formula 1.

[化學式1-1-2]

[化學式1-1-3]

[化學式1-1-4]

[化學式1-1-5]

[化學式1-1-6]

In an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1-1 to 1-1-6. [chemical formula 1-1-1]

[chemical formula 1-1-2]

[chemical formula 1-1-3]

[chemical formula 1-1-4]

[chemical formula 1-1-5]

[chemical formula 1-1-6]

In Chemical Formula 1-1-1 to Chemical Formula 1-1-6, H1 to H12 are each independently hydrogen; or deuterium, at least one of H1 to H12 is deuterium, and the definitions of other substituents are the same as those in Chemical Formula 1.

In an exemplary embodiment of the present specification, X is O; S; or CRR', and each of R and R' is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted cycloalkyl group of 3 to 30 carbon atoms; a substituted or unsubstituted heterocycloalkyl group of 2 to 30 carbon atoms; a substituted or unsubstituted heterocycloalkyl group of 6 to 30 carbon atoms substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, X is O; S; or CRR', and each of R and R' is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group of 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, X is O; S; or CRR', and R and R' are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In an exemplary embodiment of the present specification, X is O; S; or CRR', and R and R' are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, X is O; S; or CRR', and R and R' are each independently an alkyl group having 1 to 5 carbon atoms, which is unsubstituted or substituted with deuterium .

In an exemplary embodiment of the present specification, X is O; S; or CRR', and R and R' are each independently methyl, which is unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, L is a direct bond; or a substituted or unsubstituted C6 to C30 aryl group.

In an exemplary embodiment of the present specification, L is a direct bond; or a substituted or unsubstituted C6 to C12 aryl group.

In an exemplary embodiment of the present specification, L is a direct bond; substituted or unsubstituted phenylene; substituted or unsubstituted biphenylene; or substituted or unsubstituted naphthylene .

In an exemplary embodiment of the present specification, L is a direct bond; phenylene; biphenylene; or naphthylene.

In an exemplary embodiment of the present specification, L may be a direct bond or be represented by any one of the following structural formulas.

意謂三嗪及縮合咔唑各自鍵結的位置。 In the structural formula,

It means the position where each of the triazine and the condensed carbazole are bonded.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 2 to 60 carbon atoms Unsubstituted heteroaryl.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 2 to 30 carbon atoms Unsubstituted heteroaryl.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a heteroaryl group having 2 to 30 carbon atoms , which are unsubstituted or substituted and contain O or S.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are each independently an aryl group having 6 to 30 carbon atoms, which is unsubstituted or substituted by an aryl group having 6 to 20 carbon atoms; or Heteroaryl having 2 to 30 carbon atoms.

In an exemplary embodiment of the specification, Ar1 and Ar2 are each independently substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl ; substituted or unsubstituted dibenzofuryl; or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are each independently unsubstituted or substituted by an aryl group having 6 to 20 carbon atoms; unsubstituted or phenyl having 6 to 20 carbon atoms An aryl-substituted biphenyl group of carbon atoms; a terphenyl group unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms; a dibenzofuranyl group; or a dibenzothienyl group.

In an exemplary embodiment of the specification, Ar1 is substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted dibenzofuryl; or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the specification, Ar2 is substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl; substituted or unsubstituted substituted dibenzofuryl; or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the specification, when Ar1 is substituted or unsubstituted phenyl, Ar2 is substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl; substituted or unsubstituted dibenzofuryl; or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the specification, when Ar1 is substituted or unsubstituted biphenyl, Ar2 is substituted or unsubstituted biphenyl; substituted or unsubstituted dibenzofuran or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the specification, when Ar1 is a substituted or unsubstituted dibenzofuryl group, Ar2 is a substituted or unsubstituted dibenzofuryl group; or substituted or unsubstituted of dibenzothienyl.

In an exemplary embodiment of the specification, when Ar1 is substituted or unsubstituted dibenzothienyl, Ar2 is substituted or unsubstituted dibenzofuranyl; or substituted or unsubstituted of dibenzothienyl.

不一定包含氘。 In an exemplary embodiment of this specification, the chemical formula 1

Does not necessarily contain deuterium.

In the electron transport part and the hole transport part where electrons are directly exchanged, the vibration frequency of the interatomic bond in the molecule changes continuously as the electrons move, thereby affecting the stability of the interatomic bond in the molecule and the stability of the molecular structure. By substituting the compound with deuterium having a higher molecular weight than hydrogen, the energy of the molecule is lowered due to a reduction in the vibrational frequency change, and thus the stability of the molecule is enhanced.

In addition, since the single bond dissociation energy of carbon and deuterium is higher than the single bond dissociation energy of carbon and hydrogen, the thermal stability of the molecule increases, so that there is an effect of improving the service life of the device.

[化學式B]

[化學式C]

In an exemplary embodiment of the present specification, Chemical Formula 1 includes the structures of the following Chemical Formulas A and B, and optionally may include the structure of the following Chemical Formula C. [chemical formula A]

[chemical formula B]

[chemical formula C]

意謂鍵結至另一結構的位點，且 L'為具有6個至60個碳原子的經取代或未經取代之伸芳基，且其他取代基的定義與化學式1中的定義相同。 In chemical formula A to chemical formula C, each structure

means a position of bonding to another structure, and L' is a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, and the definitions of other substituents are the same as those in Chemical Formula 1.

In an exemplary embodiment of the present specification, when L of Chemical Formula 1 is a direct bond, Chemical Formula 1 may be represented by a bond of [Chemical Formula A]-[Chemical Formula B].

In an exemplary embodiment of the present specification, when L of Chemical Formula 1 is not a direct bond, Chemical Formula 1 may be represented by a bond of [Chemical Formula A]-[Chemical Formula C]-[Chemical Formula B].

In an exemplary embodiment of the present application, a heterocyclic compound is provided, wherein Chemical Formula 1 includes structures of Chemical Formula A and Chemical Formula B and optionally includes a structure of Chemical Formula C, and the deuterium content of Chemical Formula B is 50% or greater 50% and 100% or less than 100%.

In an exemplary embodiment of the present specification, the deuterium content of B may be greater than 0%, 30% or greater, 50% or greater than 50%, and 100% or less than 100%.

In an exemplary embodiment of the present specification, the deuterium content of the chemical formula A and the chemical formula C may be 0%.

In an exemplary embodiment of the present specification, the photochemical characteristics of compounds containing deuterium and compounds not containing deuterium are nearly similar, but when deposited in thin films, deuterium-containing materials tend to be packed with narrow intermolecular distances.

Therefore, when an electron-only device (EOD) and a hole-only device (HOD) were manufactured and their current densities according to voltage were confirmed, it could be confirmed that the compound of Chemical Formula 1 containing deuterium according to the present application exhibited a higher More balanced charge transport characteristics.

Furthermore, when the surface of the thin film was observed using an atomic force microscope (AFM), it was confirmed that the thin film made of the compound containing deuterium was deposited with a more uniform surface without any aggregated parts.

In an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds.

In another exemplary embodiment of the present specification, a first electrode; a second electrode; and an organic material layer having one or more layers disposed between the first electrode and the second electrode are included, and the organic material layer One or more layers include the heterocyclic compound of Chemical Formula 1.

在化學式2中， L1及L2各自獨立地為直接鍵；或具有6個至60個碳原子的經取代或未經取代之伸芳基， l1及l2各自為1至3的整數，且當l1及l2各自為2或大於2時，括弧中的取代基彼此相同或不同， R1及R2各自獨立地為氫；氘；鹵基；氰基；具有1個至60個碳原子的經取代或未經取代之烷基；具有3個至60個碳原子的經取代或未經取代之環烷基；具有2個至60個碳原子的經取代或未經取代之雜環烷基；具有6個至60個碳原子的經取代或未經取代之芳基；或具有2個至60個碳原子的經取代或未經取代之雜芳基， H為氫且D為氘，以及 d1及d2各自獨立地為0至7的整數。 In an exemplary embodiment of the present specification, the organic material layer including the heterocyclic compound may further include a compound of the following Chemical Formula 2. [chemical formula 2]

In Chemical Formula 2, L1 and L2 are each independently a direct bond; or a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, l1 and l2 are each an integer of 1 to 3, and when l1 and l2 are each 2 or greater than 2, the substituents in the brackets are the same or different, R1 and R2 are each independently hydrogen; deuterium; halogen; cyano; substituted or unsubstituted with 1 to 60 carbon atoms Substituted alkyl; substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; substituted or unsubstituted heterocycloalkyl having 2 to 60 carbon atoms; having 6 A substituted or unsubstituted aryl group of up to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group of 2 to 60 carbon atoms, H is hydrogen and D is deuterium, and d1 and d2 are each are independently an integer of 0 to 7.

In the case that the organic light-emitting device contains both the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2, better efficiency and service life effects are exhibited. From this result, it can be expected that an excited recombination phenomenon will occur when both compounds are included.

The exciton recombination phenomenon is a phenomenon in which energy having the magnitudes of the donor (p host) HOMO level and the acceptor (n host) LUMO level is released as electrons are exchanged between two molecules. When excitation recombination occurs between two molecules, reverse intersystem crossing (RISC) occurs, and the internal quantum efficiency of fluorescence can be increased to 100% due to RISC. When a donor (p host) with good hole transport capability and an acceptor (n host) with good electron transport capability are used as the host of the light-emitting layer, holes are injected into the p host and electrons are injected into the n host, The driving voltage can be reduced, which can contribute to improving the service life. In the present invention, the compound of Chemical Formula 2 serves as a donor and the compound of Chemical Formula 1 serves as an acceptor, so that it can be confirmed that when the compound is used as a host of a light emitting layer, excellent device characteristics are exhibited.

In an exemplary embodiment of the present specification, L1 and L2 are each independently a direct bond; or a substituted or unsubstituted C6-C30 arylylene group.

In an exemplary embodiment of the present specification, L1 and L2 are each independently a direct bond; or an unsubstituted or deuterium-substituted C6-C30 arylylene group.

In an exemplary embodiment of the present specification, L1 and L2 are each independently a direct bond; or an unsubstituted or deuterium-substituted C6-C12 arylylene group.

In an exemplary embodiment of the present specification, L1 and L2 are each independently a direct bond; an unsubstituted or deuterium-substituted phenylene group; or an unsubstituted or deuterium-substituted biphenylene group.

In an exemplary embodiment of the specification, R1 and R2 are each independently substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted substituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

In an exemplary embodiment of the specification, R1 and R2 are each independently substituted or unsubstituted C1 to C30 alkyl; substituted or unsubstituted C3 to C30 cycloalkyl; substituted or unsubstituted substituted C2 to C30 heterocycloalkyl; substituted or unsubstituted C6 to C30 aryl; or substituted or unsubstituted C2 to C30 heteroaryl.

In an exemplary embodiment of the specification, R1 and R2 are each independently substituted or unsubstituted C1 to C30 alkyl; substituted or unsubstituted C3 to C30 cycloalkyl; substituted or unsubstituted a substituted C6 to C30 aryl; or a substituted or unsubstituted C2 to C30 heteroaryl.

In an exemplary embodiment of the present specification, R1 and R2 are each independently a substituted or unsubstituted C6-C30 aryl group; or a substituted or unsubstituted C2-C30 heteroaryl group.

In an exemplary embodiment of the present specification, R1 and R2 are each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group containing O or S .

In an exemplary embodiment of the specification, R1 and R2 are independently substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl ; substituted or unsubstituted terphenyl; substituted or unsubstituted fluorenyl; substituted or unsubstituted dibenzofuranyl; or substituted or unsubstituted dibenzothienyl .

In an exemplary embodiment of the specification, R1 and R2 are each independently unsubstituted or deuterium-substituted phenyl; unsubstituted or deuterium-substituted biphenyl; unsubstituted or deuterium-substituted biphenyl Triphenyl; unsubstituted or deuterium-substituted extended triphenyl; unsubstituted or substituted by one or more substituents selected from deuterium and alkyl; unsubstituted or deuterium-substituted dibenzofuryl; or unsubstituted or deuterium-substituted dibenzothienyl.

In an exemplary embodiment of the present specification, R1 and R2 are each independently unsubstituted or substituted by one or more substituents selected from deuterium and alkyl from C6 to C30 aryl; or unsubstituted or Deuterium-substituted C2 to C30 heteroaryl.

In an exemplary embodiment of the present specification, d1 and d2 may each be 0 or 7 independently.

[化學式2-2]

In an exemplary embodiment of the present specification, Chemical Formula 2 may be represented by the following Chemical Formula 2-1 or Chemical Formula 2-2. [chemical formula 2-1]

[chemical formula 2-2]

In Chemical Formula 2-1 and Chemical Formula 2-2, the definition of each substituent is the same as that in Chemical Formula 2.

In an exemplary embodiment of the present specification, the deuterium content of Chemical Formula 2 is 0% to 100%.

In an exemplary embodiment of the present specification, the deuterium content of Chemistry 2 is 0% or 10% to 100%.

In an exemplary embodiment of the present specification, the deuterium content of Chemistry 2 is 0% or 30% to 100%.

In an exemplary embodiment of the present specification, the deuterium content in Chemical Formula 2 may be 0%.

In an exemplary embodiment of the present specification, the deuterium content of Chemical Formula 2 may be greater than 0% and 100% or less than 100%.

In an exemplary embodiment of the present specification, the content of deuterium in Chemical Formula 2 may be 10% to 100%.

The organic light emitting device according to an exemplary embodiment of the present specification may include the heterocyclic compound of Chemical Formula 1 having a deuterium content greater than 0% and the compound of Chemical Formula 2 having a deuterium content of 0% in the organic material layer.

The organic light emitting device according to another exemplary embodiment may include the heterocyclic compound of Chemical Formula 1 having a deuterium content greater than 0% and the compound of Chemical Formula 2 having a deuterium content greater than 0% in the organic material layer.

In an exemplary embodiment of the present specification, when the chemical formula 2 includes deuterium, compared with the case where the chemical formula 2 does not include deuterium, there are effects of reducing driving voltage and increasing luminous efficiency and service life.

Likewise, in the case of the compound of Chemical Formula 2, in the electron-transporting part where electrons are directly exchanged and the hole-transporting part, the vibration frequency of the interatomic bond in the molecule changes continuously as electrons move, thereby affecting the interatomic bond in the molecule. stability and stability of the molecular structure. By substituting the compound with deuterium having a higher molecular weight than hydrogen, the energy of the molecule is lowered due to a reduction in the vibrational frequency change, and thus the stability of the molecule is enhanced.

In addition, since the single bond dissociation energy of carbon and deuterium is higher than the single bond dissociation energy of carbon and hydrogen, the thermal stability of the molecule increases, so that there is an effect of improving the service life of the device.

。 In an exemplary embodiment of the present specification, Chemical Formula 2 may be represented by any one of the following compounds.

.

In one embodiment of the present specification, the organic material layer may comprise a weight ratio of 1:10 to 10:1, preferably a weight ratio of 1:8 to 8:1, and a weight ratio of 1:5 to 5:1. The heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 at a weight ratio of 1:3 to 3:1.

In an exemplary embodiment of the present specification, the organic material layer may include the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 in a weight ratio of 1:1 to 1:3.

In an exemplary embodiment of the present specification, the organic material layer may further include a phosphorescent dopant.

In an exemplary embodiment of the present specification, the phosphorescent dopant may be a green, blue or red phosphorescent dopant.

In an exemplary embodiment of the present specification, the phosphorescent dopant may be a green phosphorescent dopant.

In another exemplary embodiment, the phosphorescent dopant may be a red phosphorescent dopant.

In an exemplary embodiment of the present specification, the phosphorescent dopant may be an iridium dopant.

Those dopants known in the art can be used as phosphorescent dopant materials. For example, phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L ₂ MX', and L ₃ M may be used, but the scope of the present invention is not limited to these examples.

Herein, L, L', L", X' and X" are bidentate ligands different from each other, and M is a metal forming an octahedral complex.

M can be iridium, platinum, osmium, and the like.

L, L' and L" are anionic bidentate ligands coordinated by sp2 carbon and heteroatoms to M as an iridium dopant, and non-limiting examples of L, L' and L" include 1- Phenylisoquinoline, 2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenylbenzothiazole, 2-phenylbenzothiazole, 7,8-benzo Quinoline, thienylpyrazine, phenylpyridine, benzothienylpyrazine, 3-methoxy-2-phenylpyridine, thienylpyrazine, tolylidine and the like.

X' and X" may function to trap electrons or holes, and non-limiting examples of X' and X" include acetylacetonate (acac), hexafluoroacetylpyruvate, acetal base, picolinate, 8-hydroxyquinoline, and the like.

In an exemplary embodiment of the present specification, as the iridium-based dopant, Ir(ppy) ₃ which is a green phosphorescent dopant may be used.

In an exemplary embodiment of the present specification, as the iridium-based dopant, Ir(piq)2(acac), which is a red phosphorescent dopant, may be used.

In an exemplary embodiment of the present specification, based on the entire light-emitting layer, the content of the dopant may be 1% to 15%, preferably 1% to 10%.

In addition to forming an organic material layer having one or more layers by using the heterocyclic compound of Chemical Formula 1 described above alone or using the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2, according to an exemplary embodiment of the specification The organic light-emitting device of the example can be manufactured by typical methods and materials used for manufacturing organic light-emitting devices.

When manufacturing an organic light emitting device, the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 can be formed as an organic material layer not only by a vacuum deposition method but also by a solution coating method. Herein, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating method, and the like, but is not limited thereto.

The organic material layer of the organic light emitting element of the present invention may be constituted not only of a single layer structure but also of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic material layers. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller number of organic material layers.

In an exemplary embodiment of the present specification, the first electrode may be a positive electrode, and the second electrode may be a negative electrode.

In another exemplary embodiment of the present specification, the first electrode may be a negative electrode, and the second electrode may be a positive electrode.

In the organic light emitting device of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer may include the heterocyclic compound of Chemical Formula 1.

In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2.

In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host may include the heterocyclic compound of Chemical Formula 1.

In the organic light emitting element of the present specification, the heterocyclic compound of Chemical Formula 1 may be used as a green host or a red host.

In the organic light-emitting device of the present specification, the organic material layer includes a light-emitting layer, and the light-emitting layer includes a host, and the host may include the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2.

In the organic light emitting element of the present specification, the compound of Chemical Formula 2 may be used as a green host or a red host.

When the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 are combined to form a host, it exhibits better efficiency and service life than when one host is used.

In an exemplary embodiment of the present specification, the heterocyclic compound of Chemical Formula 1 may be used as an N-type host material, and the compound of Chemical Formula 2 may be used as a P-type host material.

In an exemplary embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound of Chemical Formula 1 may be used as a material of the blue organic light emitting device. For example, the heterocyclic compound of Chemical Formula 1 may be included in the host material of the light emitting layer of the blue organic light emitting device.

In another exemplary embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound of Chemical Formula 1 may be used as a material of the green organic light emitting device. For example, the heterocyclic compound of Chemical Formula 1 may be included in a host material of a light emitting layer of a green organic light emitting device.

In yet another exemplary embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound of Chemical Formula 1 may be used as a material of the red organic light emitting device. For example, the heterocyclic compound of Chemical Formula 1 may be included in a host material of a light emitting layer of a red organic light emitting device.

The organic light-emitting device of the present invention may further comprise one or more layers selected from the group consisting of: light-emitting layer, hole injection layer, hole transport layer, electron injection layer, electron transport layer, electron blocking layer and a hole blocking layer.

1 to 3 illustrate a stacking sequence of electrodes and organic material layers of an organic light emitting element according to an exemplary embodiment of the present specification. However, the scope of the present application is not intended to be limited by these drawings, and structures of organic light emitting devices known in the art can also be applied to the present application.

According to FIG. 1 , an organic light emitting element in which a positive electrode 200 , an organic material layer 300 and a negative electrode 400 are sequentially stacked on a substrate 100 is shown. However, the organic light emitting element is not limited to only this structure, and like FIG. 2 , an organic light emitting element in which a negative electrode, an organic material layer, and a positive electrode are sequentially stacked on a substrate may also be realized.

FIG. 3 exemplifies the case where the organic material layer is multilayered. The organic light emitting device according to FIG. 3 comprises a hole injection layer 301 , a hole transport layer 302 , a light emitting layer 303 , a hole blocking layer 304 , an electron transport layer 305 and an electron injection layer 306 . However, the scope of the present application is not limited by the stacked structure as described above, and if necessary, layers other than the light emitting layer may be omitted, and another desired functional layer may be further added.

The organic material layer including the heterocyclic compound of Chemical Formula 1 may additionally include other materials as necessary.

In the organic light-emitting element according to an exemplary embodiment of the present specification, materials other than the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 will be exemplified below, but these materials are provided for illustration only and do not limit the present invention. scope of the application and may be substituted by publicly known materials in the art.

As the positive electrode material, a material having a relatively high work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer, and the like can be used. Specific examples of positive electrode materials include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (indium zinc oxide; IZO); combinations of metals and oxides, such as ZnO:Al or SnO ₂ :Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylidene- 1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but not limited thereto.

As the negative electrode material, a material having a relatively low work function can be used, and a metal, a metal oxide, or a conductive polymer, and the like can be used. Specific examples of negative electrode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer construction materials such as LiF/Al or LiO ₂ /Al; and the like, but not limited thereto.

As the hole injection material, publicly known hole injection materials can also be used, and for example phthalocyanine compounds such as phthalocyanine disclosed in U.S. Patent No. 4,356,429 or literature ["Advanced Materials (Advanced Material)", 6, p. 677 (1994)] starburst amine derivatives such as tris(4-carbazinyl-9-ylphenyl)amine (TCTA), 4,4',4"-tris [Phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) , polyaniline/dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (which is a soluble conductive polymer), polyaniline/camphorsulfonic acid acid or polyaniline/poly(4-styrenesulfonate), and the like.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like can be used, and low molecular weight or polymeric materials can also be used.

As the electron transport material, oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyananthraquinone dimethane and Its derivatives, fluorenone derivatives, diphenylethylene dicyanide and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and the like, and low Molecular weight materials and polymeric materials.

As the electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

As the light emitting material, a red light emitting material, a green light emitting material or a blue light emitting material may be used, and two or more light emitting materials may be mixed and used as necessary. In this case, two or more than two luminescent materials are deposited and used as individual supplies, or premixed for deposition and used as supplies. In addition, fluorescent materials can also be used as light-emitting materials, but can also be used as phosphorescent materials. As a light-emitting material, it is also possible to use alone a material that emits light by combining holes and electrons injected from each of the positive electrode and the negative electrode, but it is also possible to use a material in which a host material and a dopant material participate in light emission together.

When mixing and using hosts of luminescent materials, hosts of the same series may also be mixed and used, and hosts of different series may also be mixed and used. For example, any two or more types of N-type host material or P-type host material can be selected and used as the host material of the light-emitting layer.

The organic light emitting element according to an exemplary embodiment of the present specification may be a top emission type, a bottom emission type, or a dual emission type according to materials to be used.

Based on principles similar to those applied to organic light-emitting elements, the compound according to an exemplary embodiment of the present specification can function even in organic electronic elements including organic solar cells, organic photoconductors, organic transistors, and the like. effect.

In addition, it is possible to finely adjust the energy band gap by introducing various substituents into the structure of Chemical Formula 1, and at the same time, it is possible to improve the characteristics at the interface between organic materials and diversify the uses of the materials.

In another exemplary embodiment of the present specification, there is provided a composition for an organic material layer of an organic light emitting device, which includes the heterocyclic compound of Chemical Formula 1.

In addition, another exemplary embodiment of the present specification provides a composition for an organic material layer of an organic light emitting device, which includes the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2.

Specific contents regarding the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 are the same as those described above.

The weight ratio of the heterocyclic compound represented by Chemical Formula 1 to the compound of Chemical Formula 2 in the composition may be 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, and 1:3 to 3 :1, but not limited to.

In an exemplary embodiment of the present specification, the composition is in a form in which two or more compounds are simply mixed, and materials in a powder state may also be mixed before forming an organic material layer of an organic light-emitting element, and it is possible Compounds that are liquid at temperatures equal to or above the suitable temperature are mixed. The composition is solid at a temperature equal to or lower than the melting point of each material, and can be maintained in liquid form when the temperature is adjusted.

In an exemplary embodiment of the present specification, the composition may be in a form in which the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 are simply mixed.

The composition may additionally contain publicly known materials in the art, such as solvents and additives.

The composition can be used when forming an organic material of an organic light-emitting device, and in particular, can be used more preferably when forming a host of a light-emitting layer.

In an exemplary embodiment of the present specification, there is provided a method of manufacturing an organic light-emitting element, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming an organic light-emitting device having one or more layers on the first electrode. a material layer; and forming a second electrode on the organic material layer, wherein the formation of the organic material layer includes forming an organic material layer having one or more layers by using a composition of the organic material layer (including a heterocyclic compound of Chemical Formula 1) .

A method of manufacturing an organic light emitting element according to another exemplary embodiment includes: preparing a substrate; forming a first electrode on the substrate; forming an organic material layer having one or more layers on the first electrode; and forming an organic material layer on the organic material layer. forming the second electrode, wherein the formation of the organic material layer includes forming an organic material layer having one or more layers by using a composition of the organic material layer including a heterocyclic compound of Chemical Formula 1 and a compound of Chemical Formula 2, and the organic The material layer may be formed by premixing the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 and using a thermal vacuum deposition method to form an organic material layer.

Pre-mixing means that before depositing the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 on the organic material layer, the materials are first mixed and the mixture is contained in one common container and mixed.

The pre-mixed material may be referred to as a composition of the organic material layer according to an exemplary embodiment of the present specification.

Hereinafter, the specification will be described in more detail in examples, but these examples are provided only for the purpose of illustrating the application and are not intended to limit the scope of the application.

1）製備中間物1-1-1 < Preparation Example > [ Preparation Example 1] Preparation of Compound 1-1

1) Preparation of intermediate 1-1-1

12H-Benzo[4,5]thieno[2,3-a]carbazole [A] (10 g, 0.037 mol), trifluoromethanesulfonic acid (34 g, 0.23 mol) and D ₆ - A mixture of benzene (200 ml) was refluxed at 70°C in a single neck round bottom flask. The resulting product was quenched and extracted with dichloromethane (DCM) and H ₂ O, concentrated, and then filtered through silica gel. The filtered product was concentrated and then treated with methanol to obtain Intermediate 1-1-1 (7.65 g, 73% yield). 2) Preparation of compound 1-1

The intermediate 1-1-1 (7.65 g, 0.027 mol), 2-chloro-4,6-diphenyl-1,3,5-triazine [B] (7.95 g, 0.030 mol), three (Dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) (2.47 grams, 0.0027 moles), tri-tertiary butylphosphine (t-Bu ₃ P) (7.00 grams, 0.035 moles ear), sodium tertiary butoxide (t-BuONa) (5.19 g, 0.054 mol) and toluene (70 mL) were placed in a single-neck round bottom flask and refluxed at 100 °C. After the resulting product was extracted with DCM and concentrated, silica gel filtration was performed, and then the filtered product was concentrated and then treated with methanol to obtain the target compound 1-1 (8.62 g, yield 62%).

62% 1-2

95% 1-3

83% 1-4

96% 1-7

83% 1-10

77% 1-13

75% 1-19

72% 1-22

93% 1-31

66% 1-37

62% 1-40

71% 1-44

92% 1-53

63% 1-57

65% 1-63

82% 1-71

78% 1-80

90% 1-83

68% 1-87

91% 1-93

58% 1-94

73% 1-95

75% 1-99

69% 1-103

59% 1-105

73% 1-106

69% 1-107

72% 1-112

63% 1-115

59% 1-121

76% 1-130

85% 1-142

82% 1-145

73% 1-156

77% 1-164

92% 1-172

81% 1-176

69% 1-187

65% 1-200

70% 1-203

76% 1-212

81% 1-226

88% 1-236

79% 1-259

63% 1-272

91% 1-285

59% 1-311

64% 1-325

91% 1-327

77% 1-332

83% 1-334

69% 1-337

75% 1-339

66% 1-341

57% 1-351

92% Except using Compound A1 and Compound B1 in Table 1 below to replace 12H-benzo[4,5]thieno[2,3-a]carbazole [A] and 2-chloro-4,6- The target compound D1 of Table 1 below was synthesized in the same manner as Production Example 1 except for diphenyl-1,3,5-triazine [B] . [Table 1] compound Compound A1 Compound B1 Compound D1 Yield 1-1

62% 1-2

95% 1-3

83% 1-4

96% 1-7

83% 1-10

77% 1-13

75% 1-19

72% 1-22

93% 1-31

66% 1-37

62% 1-40

71% 1-44

92% 1-53

63% 1-57

65% 1-63

82% 1-71

78% 1-80

90% 1-83

68% 1-87

91% 1-93

58% 1-94

73% 1-95

75% 1-99

69% 1-103

59% 1-105

73% 1-106

69% 1-107

72% 1-112

63% 1-115

59% 1-121

76% 1-130

85% 1-142

82% 1-145

73% 1-156

77% 1-164

92% 1-172

81% 1-176

69% 1-187

65% 1-200

70% 1-203

76% 1-212

81% 1-226

88% 1-236

79% 1-259

63% 1-272

91% 1-285

59% 1-311

64% 1-325

91% 1-327

77% 1-332

83% 1-334

69% 1-337

75% 1-339

66% 1-341

57% 1-351

92%

For reference purposes, intermediate compound 1-1-1 was prepared in Preparation Example 1, and according to the reaction condition test experiment carried out under the conditions shown in Experiment 1 to Experiment 4 in Table 2 below, it was confirmed that compound 1-1-1 was not synthesized. 1-1. [Table 2] experiment Compound (gram, equivalent) Solvent (ml) Catalyst (mole%) Temperature/time (℃, day) condition Amount obtained, yield 1 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) _D2O (100ml) Pt/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 2 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 3 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 200℃, 2 days Gland tube NO reaction 4 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Gland tube NO reaction

Therefore, as shown in Table 3 below, the intermediate compound 1-1-1 was synthesized under the reaction conditions of Experiment 7 having the highest substitution rate. [table 3] experiment Compound (gram, equivalent) Solvent (ml) Acid (grams, equivalent) temperature Yield Replacement rate 5 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (13.7 g, 25 equivalents) RT 96% 43% 6 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (13.7 g, 25 equivalents) 30℃ 88% 69% 7 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (13.7 g, 25 equivalents) 40℃ 71% 94% 8 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) DMSO-D6 (50ml) CF3SO3H (13.7 g, 25 equivalents) 40℃ 80% 55% 9 12H-Benzo[4,5]thieno[2,3-a]carbazole (1 g, 1 equivalent) DMF-D6 (50ml) CF3SO3H (13.7 g, 25 equivalents) 40℃ 76% 60%

In the reaction of substituting hydrogen in an organic compound with deuterium, there is a tendency that the higher the reaction temperature, the higher the substitution rate of hydrogen to deuterium and the lower the yield. Here, the substitution ratio was calculated by [(the number of substituted deuteriums after the chemical reaction)/(the number of hydrogens in the compound before the chemical reaction)]*100.

1）製備中間物2-2-1 [ Preparation Example 2] Preparation of Compound 2-2

1) Preparation of intermediate 2-2-1

In 9H,9'H-3,3'-dicarbazole (10 g, 0.030 mol), 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ [E] (7.26 g, 0.030 mol), CuI (0.57 g, 0.003 mol), trans-1,2-diaminocyclohexane (0.34 g, 0.003 mol) and K ₃ PO ₄ (12.74 g, 0.06 mol) were dissolved in 100 ml of 1,4-dioxane in a single-necked round bottom flask, and the resulting solution was refluxed at 125°C for 8 hours . After the reaction was completed, distilled water and DCM were added thereto at room temperature, extraction was performed, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (DCM:hexane=1:3) and recrystallized from methanol to obtain intermediate 2-2-1 (13.92 g, yield 94%). 2) Preparation of compound 2-2

After intermediate 2-2-1 (13.92 g, 0.028 mol), 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6 ,6'-D ₉ [E'] (6.83 g, 0.028 mol), CuI (0.53 g, 0.0028 mol), trans-1,2-diaminocyclohexane (0.32 g, 0.0028 mol) After dissolving K ₃ PO ₄ (11.89 g, 0.056 mol) in 140 ml of 1,4-dioxane in a single-neck round bottom flask, the resulting solution was refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and DCM were added thereto at room temperature, extraction was performed, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (DCM:hexane=1:3) and recrystallized from methanol to obtain the target compound 2-2 (16.14 g, yield 88%).

When Compound E and Compound E' are the same, the target compound can be synthesized immediately by adding 2 equivalents of Compound E in Preparation Example 2-1. That is, when Compound E and Compound E' are the same, the aforementioned Preparation Example 2-2 can be omitted.

88% 2-3

95% 2-5

84% 2-6

67% 2-8

83% 2-9

74% 2-12

69% 2-14

57% 2-75

68% 2-76

72% 2-77

83% 2-78

88% Except using compound E1 and compound E'1 in the following table 4 to replace 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5' in Preparation Example 2 ,6,6'-D ₉ [E] and 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ Except for [E'] , the following target compound G1 was synthesized in the same manner as in Preparation Example 2. [Table 4] compound Compound E1 Compound E'1 Compound G1 Yield 2-2

88% 2-3

95% 2-5

84% 2-6

67% 2-8

83% 2-9

74% 2-12

69% 2-14

57% 2-75

68% 2-76

72% 2-77

83% 2-78

88%

1）製備中間物2-26-1 [ Preparation Example 3] Preparation of Compound 2-26

1) Preparation of intermediate 2-26-1

A mixture of 9H, 9'H-3,3'-dicarbazole (10 g, 0.030 mol), trifluoromethanesulfonic acid (112.56 g, 0.75 mol) and D ₆ -benzene (500 ml) in a single Reflux in a round bottom flask at 40°C. The resulting product was quenched and extracted with DMC and _H2O and concentrated, and then filtered through silica gel. The filtered product was concentrated and then treated with methanol to obtain Intermediate 2-26-1 (7.07 g, 68% yield). 2) Preparation of intermediate 2-26-2

After intermediate 2-26-1 (7.07 g, 0.02 mol), CuI (0.38 g, 0.002 mol), 4-bromo-1,1'-biphenyl [E] (4.66 g, 0.02 mol) , trans-1,2-diaminocyclohexane (0.23 g, 0.002 mol) and K ₃ PO ₄ (8.49 g, 0.04 mol) were dissolved in 70 ml of 1,4- After immersion in dioxane, the resulting solution was refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and DCM were added thereto at room temperature, extraction was performed, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (DCM:hexane=1:3) and recrystallized from methanol to obtain intermediate 2-26-2 (8.28 g, yield 83%). 3) Preparation of compound 2-26

After intermediate 2-26-2 (8.28 grams, 0.017 moles), CuI (0.32 grams, 0.0017 moles), 4-bromo-1,1'-biphenyl [E'] (3.96 grams, 0.017 moles ear), trans-1,2-diaminocyclohexane (0.19 g, 0.0017 mol) and K ₃ PO ₄ (7.22 g, 0.034 mol) were dissolved in 80 ml of 1, After 4-dioxane, the resulting solution was refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and DCM were added thereto at room temperature, extraction was performed, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (DCM:hexane=1:3) and recrystallized from methanol to obtain the target compound 2-26 (8.63 g, yield 78%).

When Compound E and Compound E' are the same, the target compound can be synthesized immediately by adding 2 equivalents of Compound E in Preparation Example 3-2. That is, when Compound E and Compound E' are the same, the aforementioned Preparation Example 3-3 can be omitted.

78% 2-27

90% 2-29

74% 2-32

69% 2-33

93% In addition to using compound E2 and compound E'2 in Table 5 below to replace 4-bromo-1,1'-biphenyl [E] and 4-bromo-1,1'-biphenyl [E ] in Preparation Example 3 '] , the following target compound G2 was synthesized in the same manner as the synthesis in Preparation Example 3. [table 5] compound Compound E Compound E' Compound G2 Yield 2-26

78% 2-27

90% 2-29

74% 2-32

69% 2-33

93%

For reference purposes, the intermediate compound 2-26-1 was prepared in Preparation Example 3. According to the reaction condition test experiment carried out under the conditions shown in Experiment 1 to Experiment 4 in Table 6 below, it was confirmed that Compound 2-26-1 was not synthesized. 26-1. [Table 6] experiment Compound (gram, equivalent) Solvent (ml) Catalyst (mole%) Temperature/time (℃, day) condition Amount obtained, yield 1 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) _D2O (100ml) Pt/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 2 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 3 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 200℃, 2 days Gland tube NO reaction 4 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Gland tube NO reaction

Therefore, as shown in Table 7 below, the intermediate compound 2-26-1 was synthesized under the reaction conditions of Experiment 7 having the highest substitution rate. [Table 7] experiment Compound (gram, equivalent) Solvent (ml) Acid (grams, equivalent) temperature Yield Replacement rate 5 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (11.29 g, 25 equivalents) RT 93% 44% 6 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (11.29 g, 25 equivalents) 30℃ 82% 70% 7 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (11.29 g, 25 equivalents) 40℃ 68% 94% 8 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) DMSO-D6 (50ml) CF3SO3H (11.29 g, 25 equivalents) 40℃ 76% 61% 9 9H,9'H-3,3'-dicarbazole (1 g, 1 equivalent) DMF-D6 (50ml) CF3SO3H (11.29 g, 25 equivalents) 40℃ 78% 59%

In the reaction of substituting hydrogen in an organic compound with deuterium, there is a tendency that the higher the reaction temperature, the higher the substitution rate of hydrogen to deuterium and the lower the yield. Here, the substitution ratio was calculated by [(the number of substituted deuteriums after the chemical reaction)/(the number of hydrogens in the compound before the chemical reaction)]*100.

1）製備中間物2-50-1 [ Preparation Example 4] Preparation of Compound 2-50

1) Preparation of intermediate 2-50-1

In 9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-dicarbazole [E] (10 g, 0.021 mol), 4-bromo- 1,1'-biphenyl [F] (4.90 grams, 0.021 moles), CuI (0.40 grams, 0.0021 moles), trans-1,2-diaminocyclohexane (0.024 grams, 0.0021 moles ) and K ₃ PO ₄ (8.92 g, 0.042 mol) were dissolved in 100 ml of 1,4-dioxane in a single-neck round bottom flask, and the resulting solution was refluxed at 125° C. for 8 hours. After the reaction was completed, distilled water and DCM were added thereto at room temperature, extraction was performed, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (DCM:hexane=1:3) and recrystallized from methanol to obtain intermediate 2-50-1 (12.17 g, yield 91%). 2) Preparation of compound 2-50

A mixture of intermediate 1-50-1 (12.17 g, 0.017 mol), trifluoromethanesulfonic acid (63.78 g, 0.43 mol) and D ₆ -benzene (600 ml) was placed in a single-necked round bottom flask at 40 Reflux at °C. The resulting product was quenched and extracted with DMC and _H2O and concentrated, and then filtered through silica gel. The filtered product was concentrated and then treated with methanol to obtain the target compound 2-50 (7.62 g, 67% yield).

78% 2-51

91% 2-53

93% 2-56

76% 2-60

72% 2-62

88% 2-68

76% Except using compound E3 and compound F3 in the following table 8 to replace 9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-dicarbazole in Preparation Example 4 Except for [E] and 4-bromo-1,1'-biphenyl [F] , the following target compound G3 was synthesized in the same manner as in Preparation Example 4. [Table 8] compound Compound E3 Compound F3 Compound G3 Yield 2-50

78% 2-51

91% 2-53

93% 2-56

76% 2-60

72% 2-62

88% 2-68

76%

According to the reaction condition test experiment performed under the conditions shown in Experiment 1 to Experiment 4 in Table 9 below, it could be confirmed that Compound 2-50 was not synthesized. [Table 9] experiment Compound (gram, equivalent) Solvent (ml) Catalyst (mole%) Temperature/time (℃, day) condition Amount obtained, yield 1 2-50-1 (1 gram, 1 equivalent) _D2O (100ml) Pt/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 2 2-50-1 (1 gram, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Round bottom flask under Ar bag NO reaction 3 2-50-1 (1 gram, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 200℃, 2 days Gland tube NO reaction 4 2-50-1 (1 gram, 1 equivalent) _D2O , i-PrOH, cyclohexane (100 mL, 50 mL, 50 mL) Pt/C, Pd/C (10 mol%) 150℃, 4 days Gland tube NO reaction

Therefore, as shown in Table 10 below, compound 2-50 was synthesized under the reaction conditions of Experiment 7 having the highest substitution rate. [Table 10] test Compound (gram, equivalent) Solvent (ml) Acid (grams, equivalent) temperature Yield Replacement rate 5 2-50-1 (1 gram, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (5.89 g, 25 equivalents) RT 88% 39% 6 2-50-1 (1 gram, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (5.89 g, 25 equivalents) 30℃ 76% 53% 7 2-50-1 (1 gram, 1 equivalent) Benzene-D6 (50ml) CF3SO3H (5.89 g, 25 equivalents) 40℃ 67% 95% 8 2-50-1 (1 gram, 1 equivalent) DMSO-D6 (50ml) CF3SO3H (5.89 g, 25 equivalents) 40℃ 73% 62% 9 2-50-1 (1 gram, 1 equivalent) DMF-D6 (50ml) CF3SO3H (5.89 g, 25 equivalents) 40℃ 77% 60%

Compounds were prepared in the same manner as in Preparation Examples, and their synthesis confirmation results are shown in Table 11 and Table 12 below. Table 11 is about field desorption mass spectrometry (FD-MS) measured values, and Table 12 is about ¹ H NMR (DMSO, 300 Mz) values. [Table 11] compound FD-mass spectrometry compound FD-mass spectrometry 1-1 m/z= 514.68 (C ₃₃ H ₁₀ D ₁₀ N ₄ S=514.20) 1-2 m/z= 514.68 (C ₃₃ H ₁₀ D ₁₀ N ₄ S=514.20) 1-3 m/z= 514.68 (C ₃₃ H ₁₀ D ₁₀ N ₄ S=514.20) 1-4 m/z= 514.68 (C ₃₃ H ₁₀ D ₁₀ N ₄ S=514.20) 1-7 m/z= 590.77 (C ₃₉ H ₁₄ D ₁₀ N ₄ S=590.23) 1-10 m/z= 590.77 (C ₃₉ H ₁₄ D ₁₀ N ₄ S=590.23) 1-13 m/z= 590.77 (C ₃₉ H ₁₄ D ₁₀ N ₄ S=590.23) 1-19 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.27) 1-22 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.27) 1-31 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.27) 1-37 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-40 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-44 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-53 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-57 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-63 m/z= 620.81 (C ₃₉ H ₁₂ D ₁₀ N ₄ S ₂ =620.19) 1-71 m/z= 680.85 (C ₄₅ H ₁₆ D ₁₀ N ₄ OS=680.25) 1-80 m/z= 680.85 (C ₄₅ H ₁₆ D ₁₀ N ₄ OS=680.25) 1-83 m/z= 694.83 (C ₄₅ H ₁₄ D ₁₀ N ₄ O ₂ S=694.22) 1-87 m/z= 694.83 (C ₄₅ H ₁₄ D ₁₀ N ₄ O ₂ S=694.22) 1-93 m/z= 726.96 (C ₄₅ H ₁₄ D ₁₀ N ₄ S ₃ =726.18) 1-94 m/z= 640.83 (C ₄₅ H ₁₆ D ₁₀ N ₄ S=640.25) 1-95 m/z= 640.83 (C ₄₅ H ₁₆ D ₁₀ N ₄ S=640.25) 1-99 m/z= 590.77 (C ₃₉ H ₁₄ D ₁₀ N ₄ S=590.23] 1-103 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.27) 1-105 m/z= 640.83 (C ₄₅ H ₁₆ D ₁₀ N ₄ S=640.25) 1-106 m/z= 640.83 (C ₄₅ H ₁₆ D ₁₀ N ₄ S=640.25) 1-107 m/z= 680.85 (C ₄₅ H ₁₆ D ₁ 0N ₄ OS=680.25) 1-112 m/z= 498.61 (C ₃₃ H ₁₀ D ₁₀ N ₄ O=498.23) 1-115 m/z= 574.71 (C ₃₉ H ₁₄ D ₁₀ N ₄ O=574.26) 1-121 m/z= 574.71 (C ₃₉ H ₁₄ D ₁₀ N ₄ O=574.26) 1-130 m/z= 650.81 (C ₄₅ H ₁₈ D ₁₀ N ₄ O=650.29) 1-142 m/z= 650.81 (C ₄₅ H ₁₈ D ₁₀ N ₄ O=650.29) 1-145 m/z= 588.69 (C ₃₉ H ₁₂ D ₁₀ N ₄ O ₂ =588.24) 1-156 m/z= 588.69 (C ₃₉ H ₁₂ D ₁₀ N ₄ O ₂ =588.24) 1-164 m/z= 588.69 (C ₃₉ H ₁₂ D ₁₀ N ₄ O ₂ =588.24) 1-172 m/z= 604.75 (C ₃₉ H ₁₂ D ₁₀ N ₄ OS=604.21) 1-176 m/z= 664.79 (C ₄₅ H ₁₆ D ₁₀ N ₄ O ₂ =664.27) 1-187 m/z= 680.85 (C ₄₅ H ₁₅ D ₁₀ N ₄ OS=680.25) 1-200 m/z= 710.90 (C ₄₅ H ₁₄ D ₁₀ N ₄ OS ₂ =710.20) 1-203 m/z= 624.77 (C ₄₃ H ₁₆ D ₁₀ N ₄ O=624.27) 1-212 m/z= 624.77 (C ₄₃ H ₁₆ D ₁₀ N ₄ O=624.27) 1-226 m/z= 606.83 (C ₄₂ H ₁₄ D ₁₆ N ₄ =606.35) 1-236 m/z= 682.93 (C ₄₈ H ₁₈ D ₁₆ N ₄ =682.38) 1-259 m/z= 620.81 (C ₄₂ H ₁₂ D ₁₆ N ₄ O=620.33) 1-272 m/z= 620.81 (C ₄₂ H ₁₂ D ₁₈ N ₄ O=620.33) 1-285 m/z= 696.91 (C ₄₈ H ₁₆ D ₁₆ N ₄ O=696.36) 1-311 m/z= 656.89 (C ₄₆ H ₁₆ D ₁₆ N ₄ =656.36) 1-325 m/z= 590.77 (C ₃₉ H ₁₄ D ₁₀ N ₄ S=690.23) 1-327 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.87) 1-332 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.87) 1-334 m/z= 716.93 (C ₄₉ H ₂₀ D ₁₀ N ₄ S=716.28) 1-337 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.87) 1-339 m/z= 574.71 (C39H14D10N4O=574.26) 1-341 m/z= 650.81 (C ₄₅ H ₁₈ D ₁₀ N ₄ O=650.29) 1-351 m/z= 666.87 (C ₄₅ H ₁₈ D ₁₀ N ₄ S=666.27) 2-2 m/z= 654.91 (C48H14D18N2=654.37) 2-3 m/z= 574.79 (C42H14D14N2=574.31) 2-6 m/z= 654.91 (C48H14D18N2=654.37) 2-8 m/z= 654.91 (C48H14D18N2=654.37) 2-9 m/z= 654.91 (C48H14D18N2=654.37) 2-12 m/z= 735.03 (C54H14D22N2=734.43) 2-14 m/z= 735.03 (C54H14D22N2=734.43) 2-26 m/z= 650.88 (C48H18D14N2=650.34) 2-27 m/z= 574.79 (C42H14D14N2=574.31) 2-29 m/z= 650.88 (C48H18D14N2=650.34) 2-32 m/z= 650.88 (C48H18D14N2=650.34) 2-33 m/z= 650.88 (C48H18D14N2=650.34) 2-50 m/z= 668.99 (C48D32N2=668.46) 2-51 m/z= 588.87 (C42D28N2=588.40) 2-53 m/z= 668.99 (C48D32N2=668.46) 2-56 m/z= 668.99 (C48D32N2=668.46) 2-60 m/z= 749.12 (C54D32N2=748.51) 2-62 m/z= 749.12 (C54D36N2=748.51) 2-68 m/z= 680.96 (C48D30N2O=680.42) 2-75 m/z= 560.70 (C42H28N2=560.23) 2-76 m/z= 636.80 (C48H32N2=636.26) 2-77 m/z= 636.80 (C48H32N2=636.26) 2-78 m/z= 636.80 (C48H32N2=636.26) [Table 12] compound ¹ H NMR (DMSO, 300 Mz) 1-1 δ = 8.36 (4H, m), 7.50 (6H, m) 1-2 δ = 8.36 (4H, m), 7.50 (6H, m) 1-3 δ = 8.36 (4H, m), 7.50 (6H, m) 1-4 δ = 8.36 (4H, m), 7.50 (6H, m) 1-7 δ = 8.36 (2H, m), 7.96 (2H, d), 7.75 (2H, d), 7.41~7.50 (6H, m), 7.25 (2H, d) 1-10 δ = 8.36 (2H, m), 7.96 (2H, d), 7.75 (2H, d), 7.41~7.50 (6H, m), 7.25 (2H, d) 1-13 δ = 8.36~8.38 (3H, m), 7.94 (1H, s), 7.73~7.75 (3H, m), 7.61 (1H, d), 7.41~7.50 (6H, m) 1-19 δ = 7.96 (4H, d), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, d) 1-22 δ = 7.96 (4H, d), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, d) 1-31 δ = 8.36 (2H, m), 7.96 (2H, d), 7.75 (2H, d), 7.41~7.50 (6H, m), 7.25 (6H, m) 1-37 δ = 8.36 (2H, m), 8.08 (1H, d), 7.98 (1H, d), 7.88 (1H, d), 7.50~7.54 (5H, m), 7.31~7.39 (2H, m) 1-40 δ = 8.36 (2H, m), 8.08 (1H, d), 7.98 (1H, d), 7.88 (1H, d), 7.50~7.54 (5H, m), 7.31~7.39 (2H, m) 1-44 δ = 8.36 (2H, m), 7.98~8.03 (2H, m), 7.76~7.82 (2H, m), 7.50~7.54 (4H, m), 7.31~7.39 (2H, m) 1-53 δ = 8.36 (2H, m), 7.98 (1H, d), 7.79~7.88 (3H, m), 7.50~7.54 (4H, m), 7.31~7.39 (2H, m) 1-57 δ = 8.36 (2H, m), 7.98 (1H, d), 7.82 (1H, d), 7.69 (1H, d), 7.50~7.57 (5H, m), 7.31~7.39 (2H, m) 1-63 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20~8.24 (2H, m), 7.93~7.94 (2H, d), 7.49~7.56 (5H, m) 1-71 δ = 7.96~8.03 (4H, m), 7.75~7.82 (4H, m), 7.25~7.54 (8H, m) 1-80 δ = 8.38 (1H, d), 8.08 (1H, d), 7.94~7.98 (3H, m), 7.73~7.75 (3H, m), 7.31~7.61 (8H, m) 1-83 δ = 7.98 (2H, m), 7.76~7.88 (3H, m), 7.51~7.54 (3H, m), 7.31~7.39 (4H, m) 1-87 δ = 7.98~8.03 (4H, m), 7.76~7.82 (4H, m), 7.54 (2H, d), 7.31~7.39 (4H, m) 1-93 δ = 8.45 (2H, d), 8.12 (1H, s), 7.93~8.03 (6H, m), 7.68 (1H, t), 7.49~7.56 (4H, m) 1-94 δ = 8.95 (1H, d), 8.50 (1H, d), 8.36~8.38 (3H, m), 8.20 (1H, d), 8.09 (1H, d), 7.94 (1H, s), 7.73~7.77 ( 2H, m), 7.50~7.61 (5H, m), 7.39 (1H, t) 1-95 δ = 8.36~8.38 (3H, m), 7.94~8.09 (4H, m), 7.73 (1H, t), 7.50~7.63 (7H, m), 7.38 (1H, d) 1-99 δ = 8.36 (4H, m), 8.21~8.24 (2H, m), 7.60~7.68 (2H, m), 7.50 (6H, m) 1-103 δ = 8.36~8.38 (3H, m), 8.21~8.24 (2H, m), 7.94 (1H, s), 7.60~7.75 (6H, m), 7.41~7.50 (6H, m) 1-105 δ = 8.93 (1H, d), 8.36 (4H, m), 8.22 (1H, d), 8.10 (1H, d), 8.00 (1H, t), 7.79 (1H, t), 7.60 (1H, d) , 7.50 (6H, m) 1-106 δ = 9.09 (1H, s), 8.49 (1H, d), 8.36 (4H, m), 8.03 (1H, d), 7.93 (1H, d), 7.83 (1H, s), 7.50 (6H, m) , 7.36 (1H, d) 1-107 δ = 8.36 (4H, m), 8.21~8.24 (2H, m), 7.98 (1H, d), 7.79~7.88 (3H, m), 7.50~7.68 (6H, m), 7.31~7.39 (2H, m ) 1-112 δ = 8.36 (4H, m), 7.50 (6H, m) 1-115 δ = 8.36 (2H, m), 7.96 (2H, d), 7.75 (2H, d), 7.41~7.50 (6H, m), 7.25 (2H, d) 1-121 δ = 8.36~8.38 (3H, m), 7.94 (1H, s), 7.73~7.75 (3H, m), 7.61 (1H, d), 7.41~7.50 (6H, m) 1-130 δ = 7.96 (4H, d), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, d) 1-142 δ = 7.96 (4H, d), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, d) 1-145 δ = 8.36 (2H, m), 8.08 (1H, d), 7.98 (1H, d), 7.88 (1H, d), 7.50~7.54 (5H, m), 7.31~7.39 (2H, m) 1-156 δ = 8.36 (2H, m), 7.98~8.03 (2H, m), 7.76~7.82 (2H, m), 7.50~7.54 (4H, m), 7.31~7.39 (2H, m) 1-164 δ = 8.36 (2H, m), 7.98 (1H, d), 7.82 (1H, d), 7.69 (1H, d), 7.50~7.57 (5H, m), 7.31~7.39 (2H, m) 1-172 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20~8.24 (2H, m), 7.93~7.94 (2H, d), 7.49~7.56 (5H, m) 1-176 δ = 8.08 (1H, d), 7.88~7.98 (4H, m), 7.75 (2H, d), 7.25~7.54 (9H, m) 1-187 δ = 8.45 (1H, d), 7.93~8.03 (5H, m), 7.68~7.75 (3H, m), 7.41~7.56 (5H, m), 7.25 (2H, d) 1-200 δ = 8.45 (1H, d), 8.12 (2H, s), 7.92~7.99 (6H, m), 7.49~7.56 (4H, m) 1-203 δ = 8.36~8.38 (3H, m), 7.94~8.09 (4H, m), 7.73 (1H, t), 7.50~7.63 (7H, m), 7.38 (1H, d) 1-212 δ = 8.97 (1H, d), 8.36 (4H, m), 8.24 (1H, d), 8.12 (1H, d), 7.79 (1H, d), 7.50~7.59 (8H, m) 1-226 δ = 8.36 (2H, m), 7.96 (2H, d), 7.75 (2H, d), 7.41~7.50 (6H, m), 7.25 (2H, d) 1-236 δ = 7.96 (4H, d), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, d) 1-259 δ = 8.36 (2H, m), 7.98~8.03 (2H, m), 7.76~7.82 (2H, m), 7.50~7.54 (4H, m), 7.31~7.39 (2H, m) 1-272 δ = 8.36 (2H, m), 7.98 (1H, d), 7.82 (1H, d), 7.69 (1H, d), 7.50~7.57 (5H, m), 7.31~7.39 (2H, m) 1-285 δ = 8.08 (1H, d), 7.88~7.98 (4H, m), 7.75 (2H, d), 7.25~7.54 (9H, m) 1-311 δ = 8.36~8.38 (3H, m), 7.94~8.09 (4H, m), 7.73 (1H, t), 7.50~7.63 (7H, m), 7.38 (1H, d) 1-325 δ = 8.36 (4H, m), 8.21~8.24 (2H, m), 7.60~7.68 (2H, m), 7.50 (6H, m) 1-327 δ = 8.36~8.38 (5H, m), 8.21 (1H, s), 7.94 (1H, s), 7.60~7.73 (4H, m), 7.47~7.50 (7H, m) 1-332 δ = 8.36~8.38 (5H, m), 8.21 (1H, s), 7.94 (1H, s), 7.60~7.73 (4H, m), 7.47~7.50 (7H, m) 1-334 δ = 8.36 (2H, m), 8.21~8.24 (2H, m), 7.96~8.09 (5H, m), 7.50~7.68 (8H, m), 7.38 (1H, d), 7.25 (2H, d) 1-337 δ = 8.36 (2H, m), 8.21~8.24 (2H, m), 7.96 (2H, d), 7.60~7.75 (4H, m), 7.41~7.50 (6H, m), 7.25 (2H, d) 1-339 δ = 8.36 (4H, m), 8.21~8.24 (2H, m), 7.60~7.68 (2H, m), 7.50 (6H, m) 1-341 δ = 8.36~8.38 (3H, m), 8.21 (1H, s), 7.94 (1H, s), 7.60~7.73 (4H, m), 7.47~7.50 (7H, m) 1-351 δ = 8.36 (2H, m), 8.21~8.24 (2H, m), 7.96 (2H, d), 7.60~7.75 (4H, m), 7.41~7.50 (6H, m), 7.25 (2H, d) 2-2 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-3 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-6 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-8 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-9 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-12 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-14 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (4H, m), 7.77 (1H, d), 7.50~7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, t) 2-26 δ = 7.91~7.92 (8H, m), 7.75 (4H, d), 7.41~7.49 (6H, m) 2-27 δ = 8.21 (1H, s), 7.41~7.68 (13H, m) 2-29 δ = 7.91~7.94 (5H, m), 7.73~7.75 (3H, t), 7.41~7.62 (10H, m) 2-32 δ = 8.21 (2H, s), 7.60~7.75 (8H, m), 7.41~7.49 (8H, m) 2-33 δ = 8.21 (1H, s), 7.91~7.92 (4H, m), 7.75~7.68 (6H, m), 7.41~7.49 (7H, m) 2-50 δ = 100% deuterium content, no ¹ H NMR peaks 2-51 δ = 100% deuterium content, no ¹ H NMR peaks 2-53 δ = 100% deuterium content, no ¹ H NMR peaks 2-56 δ = 100% deuterium content, no ¹ H NMR peaks 2-60 δ = 100% deuterium content, no ¹ H NMR peaks 2-62 δ = 100% deuterium content, no ¹ H NMR peaks 2-68 δ = 100% deuterium content, no ¹ H NMR peaks 2-75 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.21 (3H, m), 7.89~7.99 (4H, m), 7.35~7.77 (17H, m), 7.16~7.20 (2H, t ) 2-76 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (9H, m), 7.73~7.77 (4H, m), 7.35~7.62 (13H, m ), 7.16~7.20 (2H, m) 2-77 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.21 (4H, m), 7.89~7.99 (4H, m), 7.35~7.77 (20H, m), 7.16~7.20 (2H, t ) 2-78 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (12H, m), 7.75~7.77 (5H, m), 7.58 (1H, d), 7.35~7.50 (8H, m), 7.16~7.20 (2H, m)

製備化合物 [A] -1 [ Comparative Example Preparation Example 5]

Preparation of Compound [A] -1

2,4,6-trichloro-1,3,5-triazine (10 g, 0.054 mol), (phenyl-d5)boronic acid (7.49 g, 0.059 mol), Pd(PPh ₃ ) ₄ ( A mixture of 3.12 g, 0.0027 mol), K ₂ CO ₃ (14.93 g, 0.11 mol), and tetrahydrofuran (100 ml)/water (30 ml) was refluxed at 120°C in a single-neck round bottom flask. The resulting product was cooled, and then concentrated and filtered with silica gel to obtain Compound [A]-1 (6.99 g, 56%). Preparation of compound [A]-2

2,4-dichloro-6-(phenyl-d5)-1,3,5-triazine (6.99 grams, 0.030 moles), (phenyl-d5)boronic acid (4.19 grams, 0.033 moles), Pd(PPh ₃ ) ₄ (1.73 g, 0.0015 mol), K ₂ CO ₃ (8.29 g, 0.06 mol) and tetrahydrofuran (70 ml)/water (20 ml) mixture in a single-necked round bottom flask at 120 Reflux at °C. The resulting product was cooled, and then concentrated and filtered with silica gel to obtain compound [A]-2 (5.58 g, 67%). Preparation of compound [C]-1

12H-Benzo[4,5]thieno[2,3-a]carbazole (10 g, 0.037 mol), trifluoromethanesulfonic acid (34 g, 0.23 mol) and D6-benzene (200 ml ) in a single-necked round-bottom flask at reflux at 70 °C. The resulting product was quenched and extracted with dichloromethane (DCM) and H ₂ O, concentrated, and then filtered through silica gel. The filtered product was concentrated and then treated with methanol to obtain compound [C]-1 (7.65 g, 73%). Preparation of Compound 3-1[H]

The mixture 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine (5.58 g, 0.020 mol), 12H-benzo[4,5]thieno[2,3 -a]carbazole-1,2,3,4,5,6,7,8,9,10-d10 (6.24 g, 0.022 mol), tris(benzylideneacetone)dipalladium(0) (Pd ₂ (dba) ₃ ) (0.92 g, 0.001 mol), tri-tertiary butylphosphine (t-Bu ₃ P) (6.00 g, 0.030 mol), tertiary sodium butoxide (t-BuONa) (5.77 g, 0.060 mol) and toluene (60 mL) were placed in a single neck round bottom flask and refluxed at 100°C. After the resulting product was extracted with dichloromethane (DCM) and concentrated, silica gel filtration was performed, and then the filtered product was concentrated and then treated with methanol to obtain the target compound 3-1[H] (8.19 g, yield 78% ).

When Compound A and Compound A' are the same, A-2 can be synthesized immediately by adding 2 equivalents of Compound A in the first reaction. That is, when A and A' are the same, the second reaction step can be omitted.

78% 3-2

68% 3-3

87% 3-4

55% 3-5

65% 3-6

71% 3-7

88% 3-8

51% 3-9

63% 3-10

79% 3-11

83% 3-12

77% 3-13

65% 3-14

57% 3-15

69% 3-16

58% Compound H in Table 13 below was synthesized in the same manner as in Comparative Example Preparation Example 5, except that other Intermediate A, Intermediate A′, Intermediate B, and Intermediate C were used in Comparative Example Preparation Example 5. [Table 13] compound A A' B C h Yield 3-1

78% 3-2

68% 3-3

87% 3-4

55% 3-5

65% 3-6

71% 3-7

88% 3-8

51% 3-9

63% 3-10

79% 3-11

83% 3-12

77% 3-13

65% 3-14

57% 3-15

69% 3-16

58%

製備化合物 [A] -1 [ Comparative Example Preparation Example 6] Preparation of Compound 3-21 (I)

Preparation of Compound [A] -1

2,4,6-trichloro-1,3,5-triazine (10 g, 0.054 mol), (phenyl-d5)boronic acid (7.49 g, 0.059 mol), Pd(PPh ₃ ) ₄ ( A mixture of 3.12 g, 0.0027 mol), K ₂ CO ₃ (14.93 g, 0.11 mol), and tetrahydrofuran (100 ml)/water (30 ml) was refluxed at 120°C in a single-neck round bottom flask. The resulting product was cooled, and then concentrated and filtered with silica gel to obtain Compound [A]-1 (6.99 g, 56%). Preparation of compound [A]-2

2,4-dichloro-6-(phenyl-d5)-1,3,5-triazine (6.99 grams, 0.030 moles), (phenyl-d5)boronic acid (4.19 grams, 0.033 moles), Pd(PPh ₃ ) ₄ (1.73 g, 0.0015 mol), K ₂ CO ₃ (8.29 g, 0.06 mol) and tetrahydrofuran (70 ml)/water (20 ml) mixture in a single-necked round bottom flask at 120 Reflux at °C. The resulting product was cooled, and then concentrated and filtered with silica gel to obtain compound [A]-2 (5.58 g, 67%). Preparation of Compound 3 - 21[I]

The mixture [A]-2 (5.58 g, 0.020 mol), 12H-benzo[4,5]thieno[2,3-a]carbazole [B] (6.01 g, 0.022 mol), tri( Dibenzylideneacetone) Dipalladium (0) (Pd ₂ (dba) ₃ ) (0.92 grams, 0.001 moles), three-tertiary butylphosphine (t-Bu ₃ P) (6.00 grams, 0.030 moles ), sodium tertiary butoxide (t-BuONa) (5.77 g, 0.060 mol) and toluene (60 mL) were placed in a single-neck round bottom flask and refluxed at 100 °C. After the resulting product was extracted with dichloromethane (DCM) and concentrated, silica gel filtration was performed, and then the filtered product was concentrated and then treated with methanol to obtain the target compound 3-21[I] (7.41 g, yield 72% ).

When Compound A and Compound A' are the same, A-2 can be synthesized immediately by adding 2 equivalents of Compound A in the first reaction. That is, when A and A' are the same, the second reaction step can be omitted.

72% 3-22

61% 3-23

59% 3-24

55% The following Compound I was synthesized in the same manner as in the synthesis of Comparative Example Preparation Example 6, except that Intermediate A, Intermediate A', Intermediate B, and Intermediate C in Table 14 below were used in Comparative Example Preparation Example 6. [Table 14] compound A A' B C I Yield 3-21

72% 3-22

61% 3-23

59% 3-24

55%

For reference purposes, Preparative Example 1 to Preparative Example 4 described above are easier to synthesize than Comparative Preparative Example 5 and Comparative Example Preparative Example 6. In addition, the cost of the reagents used in synthesizing [A]-1 and [A]-2 in Comparative Example 5 and Comparative Example 6 is extremely high. Furthermore, when synthesizing [A]-1 and [A]-2, wherein compound A or mixture A' is bonded to all three substituents of 2,4,6-trichloro-1,3,5-triazine A large amount of substances are synthesized as impurities, so that the selectivity of the reaction is also reduced. Considering the simplicity of synthesis, cost and efficiency, it can be confirmed that compared with the structures of Preparation Example 5 and Example 6 of Comparative Example, the structure of the heterocyclic compound in Chemical Formula 1 of the present invention is more advantageous in terms of manufacturing process.

< Experimental Example 1> 1 ) Manufacture of Organic Light-Emitting Element A glass substrate coated with ITO thinly to have a thickness of 1,500 angstroms was ultrasonically cleaned with distilled water. After completion of washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as acetone, methanol, and isopropanol, dried and then UVO-treated using UV in a UV cleaner for 5 minutes. Afterwards, the substrate was transferred to a plasma washer (PT), and then plasma treated under vacuum for ITO work function and to facilitate removal of residual film, and transferred to thermal deposition equipment for organic deposition.

As a common layer, the hole injection layer 4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and the hole transport layer N,N'-bis(1 -Naphthyl)-N,N′-diphenyl-(1,1′-biphenylyl)-4,4′-diamine (NPB) was formed on an ITO transparent electrode (positive electrode).

A light-emitting layer was thermally vacuum-deposited thereon as follows. By using the compound described in Table 15 below as a host and tris(2-phenylpyridine) iridium (Ir(ppy) ₃ ) as a green phosphorescent dopant doped with an amount of 7% Ir(ppy) ₃ to The host was deposited to have a thickness of 400 Angstroms. Afterwards, bathocuproine (BCP) was deposited to have a thickness of 60 Å as a hole blocking layer, and Alq ₃ was deposited thereon to have a thickness of 200 Å as an electron transport layer. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to have a thickness of 10 angstroms to form an electron injection layer, and then an aluminum (Al) negative electrode was deposited on the electron injection layer to have a thickness of 1200 angstroms to form Negative electrode, thereby fabricating organic electroluminescent elements.

2 ）有機電致發光元件的驅動電壓及發光效率 At the same time, all organic compounds required for manufacturing OLED elements were subjected to vacuum sublimation purification for each material at 10 ⁻⁸ Torr to 10 ⁻⁶ Torr, and used to manufacture OLEDs. [comparative example]

2 ) Driving voltage and luminous efficiency of organic electroluminescent elements

For the organic electroluminescent element manufactured as described above, electroluminescence (EL) characteristics were measured by M7000 manufactured by McScience Inc., and based on the measurement results, when the reference luminance was 6,000 candela T ₉₀ is measured per square meter by a service life measuring device (M6000) manufactured by Mack Scientific.

The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE) and service life of the organic light-emitting device manufactured according to the present invention are shown in Table 15 below. [Table 15] compound Drive Voltage (Volts) Efficiency (cd/area) Color coordinates (x, y) Service life (T ₉₀ ) Comparative example 1 3-1 5.22 43.0 (0.275, 0.671) 72 Comparative example 2 3-2 5.13 43.7 (0.276, 0.673) 74 Comparative example 3 3-3 5.78 44.2 (0.284, 0.668) 75 Comparative example 4 3-4 5.66 44.1 (0.280, 0.674) 73 Comparative Example 5 3-5 5.72 44.9 (0.271, 0.673) 71 Comparative example 6 3-6 5.83 43.8 (0.284, 0.659) 68 Comparative Example 7 3-7 5.43 43.2 (0.268, 0.651) 66 Comparative Example 8 3-8 5.28 44.6 (0.284, 0.676) 63 Comparative Example 9 3-9 5.33 43.8 (0.254, 0.656) 68 Comparative Example 10 3-10 5.35 42.6 (0.275, 0.667) 69 Comparative Example 11 3-11 5.24 45.0 (0.268, 0.681) 75 Comparative Example 12 3-12 5.03 44.2 (0.274, 0.675) 77 Comparative Example 13 3-13 5.18 43.8 (0.266, 0.671) 65 Comparative Example 14 3-14 5.23 42.3 (0.268, 0.674) 68 Comparative Example 15 3-15 5.62 43.7 (0.263, 0.676) 74 Comparative Example 16 3-16 5.46 45.2 (0.284, 0.675) 70 Comparative Example 17 3-17 6.11 42.1 (0.263, 0.677) 65 Comparative Example 18 3-18 6.42 42.6 (0.285, 0.678) 62 Comparative Example 19 3-19 6.07 41.7 (0.271, 0.675) 69 Comparative Example 20 3-20 6.23 43.2 (0.282, 0.673) 66 Comparative Example 21 3-21 6.29 42.3 (0.275, 0.657) 63 Comparative Example 22 3-22 6.40 40.9 (0.665, 0.253) 58 Comparative Example 23 3-23 6.38 41.8 (0.624, 0.269) 63 Comparative Example 24 3-24 6.22 42.5 (0.265, 0.686) 56 Example 1 1-1 4.17 95.2 (0.244, 0.637) 145 Example 2 1-2 4.12 90.5 (0.269, 0.621) 149 Example 3 1-3 4.03 87.9 (0.254, 0.643) 155 Example 4 1-4 3.68 83.2 (0.245, 0.673) 157 Example 5 1-7 3.77 90.3 (0.257, 0.645) 168 Example 6 1-10 3.89 91.5 (0.264, 0.641) 166 Example 7 1-13 3.66 88.7 (0.251, 0.614) 162 Example 8 1-19 3.59 89.2 (0.264, 0.658) 158 Example 9 1-22 3.75 90.2 (0.255, 0.645) 152 Example 10 1-31 3.84 91.3 (0.259, 0.704) 154 Example 11 1-37 3.93 92.2 (0.247, 0.656) 159 Example 12 1-40 3.72 94.7 (0.256, 0.634) 161 Example 13 1-44 3.53 89.2 (0.267, 0.625) 163 Example 14 1-53 3.62 87.2 (0.258, 0.620) 155 Example 15 1-57 3.69 88.5 (0.253, 0.723) 158 Example 16 1-63 3.56 90.2 (0.243, 0.612) 153 Example 17 1-71 4.13 93.7 (0.264, 0.667) 172 Example 18 1-80 4.02 91.2 (0.252, 0.625) 166 Example 19 1-83 3.51 87.6 (0.247, 0.656) 162 Example 20 1-87 3.62 89.3 (0.244, 0.643) 158 Example 21 1-93 3.77 92.3 (0.264, 0.652) 145 Example 22 1-94 4.20 94.2 (0.264, 0.623) 154 Example 23 1-95 4.10 91.7 (0.254, 0.654) 166 Example 24 1-99 3.63 94.7 (0.254, 0.703) 162 Example 25 1-103 3.72 95.0 (0.243, 0.627) 159 Example 26 1-105 4.11 88.7 (0.264, 0.730) 170 Example 27 1-106 3.83 87.3 (0.262, 0.645) 168 Example 28 1-107 3.54 86.4 (0.253, 0.634) 152 Example 29 1-112 4.13 80.2 (0.256, 0.632) 137 Example 30 1-115 4.05 87.6 (0.258, 0.687) 122 Example 31 1-121 4.35 85.5 (0.235, 0.641) 138 Example 32 1-130 4.22 84.9 (0.237, 0.613) 131 Example 33 1-142 4.39 83.2 (0.243, 0.613) 135 Example 34 1-145 4.47 81.6 (0.253, 0.627) 120 Example 35 1-156 4.23 84.7 (0.255, 0.712) 128 Example 36 1-164 4.12 89.2 (0.242, 0.627) 132 Example 37 1-172 4.38 88.3 (0.264, 0.744) 136 Example 38 1-176 4.25 85.4 (0.234, 0.613) 140 Example 39 1-187 4.36 82.6 (0.246, 0.643) 134 Example 40 1-200 4.42 83.7 (0.257, 0.619) 122 Example 41 1-203 4.08 86.7 (0.256, 0.724) 132 Example 42 1-212 4.23 87.2 (0.245, 0.623) 142 Example 43 1-226 4.77 66.2 (0.267, 0.731) 95 Example 44 1-236 4.83 68.7 (0.251, 0.713) 100 Example 45 1-259 4.91 70.2 (0.242, 0.665) 103 Example 46 1-272 4.66 69.3 (0.257, 0.633) 97 Example 47 1-285 4.87 67.5 (0.265, 0.642) 91 Example 48 1-311 4.56 69.3 (0.251, 0.634) 93 Example 49 1-325 3.12 110.3 (0.257, 0.671) 175 Example 50 1-327 3.54 100.6 (0.265, 0.651) 163 Example 51 1-332 3.44 108.9 (0.287, 0.674) 152 Example 52 1-334 3.05 105.5 (0.271, 0.673) 148 Example 53 1-337 3.28 106.2 (0.276, 0.663) 166 Example 54 1-339 3.26 95.6 (0.244, 0.622) 163 Example 55 1-341 3.42 98.7 (0.263, 0.625) 158 Example 56 1-351 3.33 100.5 (0.253, 0.624) 172

Referring to the results in Table 15, it can be seen that the organic light-emitting device including the heterocyclic compound of the present invention has excellent driving voltage, luminous efficiency, and service life compared with the comparative example. In particular, it can be confirmed that the higher the deuterium substitution rate, the lower the driving voltage and the better the lifetime characteristics.

In particular, the case where deuterium is contained only in a specific position as in the present invention provides organic light emission having a lower driving voltage, higher luminous efficiency, and longer service life, compared to a comparative example in which a compound not containing deuterium is used. element. This is because the compounds of the present invention are substituted with deuterium having a higher molecular weight than hydrogen to reduce vibrational frequency changes and lower molecular energy, and thereby enhance molecular stability. In addition, since the single bond dissociation energy of carbon and deuterium is higher than the single bond dissociation energy of carbon and hydrogen, it can be confirmed that the service life of the device is improved as the thermal stability of the molecule increases.

In the case where the compound is contained only in a specific position as in Chemical Formula 1 of the present invention, the deuterium-containing material tends to be packed with a narrow intermolecular distance when the compound is deposited on a silicon wafer. Furthermore, when the surface of the thin film was observed using an atomic force microscope (AFM), it was confirmed that the thin film made of the compound containing deuterium was deposited with a more uniform surface without any aggregated parts.

In addition, when an organic light emitting element is driven, molecules are thermally damaged by transfer of electrons. Specifically, defects are likely to occur in oxygen and sulfur, which are the most unstable sites of Chemical Formula 1 of the present invention. The compound corresponding to Chemical Formula 1 of the present invention prevents the possibility by substituting the core structure of the heterocyclic compound with deuterium having a larger molecular weight than hydrogen to reduce the vibration frequency change and lower the molecular energy, and thus, it is possible to confirm the molecular The stability is enhanced and thus the service life of the element is significantly enhanced compared to the comparative example.

In other words, it was confirmed that when the heterocyclic compound of Chemical Formula 1 of the present invention was used as the host of the light emitting layer, the driving voltage, luminous efficiency, and service life were obviously excellent.

< Experimental Example 2> 1 ) Manufacture of Organic Light-Emitting Element A glass substrate coated with ITO thinly to have a thickness of 1,500 angstroms was ultrasonically cleaned with distilled water. After completion of washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as acetone, methanol, and isopropanol, dried and then UVO-treated using UV in a UV cleaner for 5 minutes. Afterwards, the substrate was transferred to a plasma washer (PT), and then plasma treated under vacuum for ITO work function and to facilitate removal of residual film, and transferred to thermal deposition equipment for organic deposition.

As a common layer, the hole injection layer 4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and the hole transport layer N,N'-bis(1 -Naphthyl)-N,N′-diphenyl-(1,1′-biphenylyl)-4,4′-diamine (NPB) was formed on an ITO transparent electrode (positive electrode).

A light-emitting layer was thermally vacuum-deposited thereon as follows. After premixing a type of heterocyclic compound of Chemical Formula 1 and a type of compound of Chemical Formula 2 as a host, the light-emitting layer is deposited to have a thickness of 400 angstroms in a supply source, and then by using an amount of 7% of the deposited thickness of Ir(ppy) ₃ was deposited as a green phosphorescent dopant doped host. After that, BCP was deposited to have a thickness of 60 Å as a hole blocking layer, and Alq ₃ was deposited thereon to have a thickness of 200 Å as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to have a thickness of 10 Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) negative electrode was deposited to have a thickness of 1,200 Å on the electron injection layer to form Negative electrode, thereby fabricating organic electroluminescent elements.

At the same time, all organic compounds required for manufacturing OLED elements were subjected to vacuum sublimation purification for each material at 10 ⁻⁸ Torr to 10 ⁻⁶ Torr, and used to manufacture OLEDs.

For the organic electroluminescence element manufactured as described above, electroluminescence (EL) characteristics were measured by M7000 manufactured by Mic Scientific, and based on the measurement results thereof, when the reference luminance was 6,000 cd/m2, T ₉₀ was measured by a service life measuring device (M6000) manufactured by Micro Scientific Corporation.

The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE) and service life of the organic light emitting device manufactured according to the present invention are shown in Table 16 below. [Table 16]    Light-emitting layer compound ratio Drive Voltage (Volts) Efficiency (cd/area) Color coordinates (x, y) service life (T ₉₀ ) Comparative Example 25 3-1 : 2-53 1 : 1 4.03 63.2 (0.245, 0.633) 185 Comparative Example 26 1 : 2 4.15 62.5 (0.266, 0.621) 193 Comparative Example 27 1 : 3 4.22 60.3 (0.253, 0.694) 203 Comparative Example 28 3-2 : 2-62 1 : 1 4.31 70.2 (0.245, 0.675) 163 Comparative Example 29 1 : 2 4.35 69.3 (0.257, 0.643) 172 Comparative Example 30 1 : 3 4.42 68.7 (0.264, 0.642) 183 Comparative Example 31 3-3 : 2-56 1 : 1 4.25 71.3 (0.257, 0.671) 171 Comparative Example 32 1 : 2 4.36 70.5 (0.237, 0.645) 173 Comparative Example 33 1 : 3 4.39 69.8 (0.236, 0.624) 182 Comparative Example 34 3-4 : 2-50 1 : 1 4.28 74.9 (0.255, 0.627) 204 Comparative Example 35 1 : 2 4.35 74.1 (0.252, 0.623) 213 Comparative Example 36 1 : 3 4.41 73.2 (0.257, 0.714) 224 Comparative Example 37 3-5 : 2-53 1 : 1 4.15 70.1 (0.244, 0.645) 175 Comparative Example 38 1 : 2 4.26 69.2 (0.261, 0.762) 183 Comparative Example 39 1 : 3 4.33 68.3 (0.254, 0.623) 191 Comparative Example 40 3-6 : 2-62 1 : 1 4.22 66.2 (0.254, 0.657) 230 Comparative Example 41 1 : 2 4.28 65.5 (0.277, 0.655) 237 Comparative Example 42 1 : 3 4.31 64.7 (0.263, 0.642) 241 Comparative Example 43 3-7 : 2-51 1 : 1 4.02 72.2 (0.256, 0.633) 236 Comparative Example 44 1 : 2 4.11 71.3 (0.258, 0.632) 244 Comparative Example 45 1 : 3 4.19 70.5 (0.251, 0.684) 251 Comparative Example 46 3-7 : 2-75 1 : 1 4.13 67.0 (0.235, 0.653) 193 Comparative Example 47 1 : 2 4.23 66.2 (0.236, 0.628) 201 Comparative Example 48 1 : 3 4.32 65.9 (0.258, 0.691) 213 Comparative Example 49 3-8 : 2-62 1 : 1 4.05 71.3 (0.261, 0.740) 189 Comparative Example 50 1 : 2 4.13 70.2 (0.233, 0.623) 199 Comparative Example 51 1 : 3 4.22 69.3 (0.248, 0.644) 203 Comparative Example 52 3-9 : 2-53 1 : 1 4.32 73.9 (0.257, 0.629) 215 Comparative Example 53 1 : 2 4.39 73.5 (0.254, 0.726) 223 Comparative Example 54 1 : 3 4.41 72.2 (0.245, 0.625) 233 Comparative Example 55 3-10 : 2-62 1 : 1 4.55 73.6 (0.263, 0.732) 228 Comparative Example 56 1 : 2 4.59 72.8 (0.257, 0.653) 231 Comparative Example 57 1 : 3 4.62 71.3 (0.285, 0.659) 235 Comparative Example 58 3-11 : 2-60 1 : 1 4.37 71.3 (0.268, 0.655) 246 Comparative Example 59 1 : 2 4.41 70.1 (0.287, 0.673) 249 Comparative example 60 1 : 3 4.49 69.5 (0.254, 0.626) 256 Comparative Example 61 3-12 : 2-51 1 : 1 4.33 69.3 (0.279, 0.657) 189 Comparative Example 62 1 : 2 4.38 68.8 (0.268, 0.686) 193 Comparative Example 63 1 : 3 4.42 68.2 (0.274, 0.665) 211 Comparative Example 64 3-13 : 2-68 1 : 1 4.11 67.5 (0.263, 0.672) 173 Comparative Example 65 1 : 2 4.25 66.3 (0.262, 0.654) 182 Comparative Example 66 1 : 3 4.29 65.2 (0.263, 0.676) 195 Comparative Example 67 3-14 : 2-68 1 : 1 4.13 66.5 (0.257, 0.645) 177 Comparative Example 68 1 : 2 4.21 65.2 (0.263, 0.625) 182 Comparative Example 69 1 : 3 4.25 64.2 (0.256, 0.625) 188 Comparative example 70 3-15 : 2-51 1 : 1 4.52 70.5 (0.254, 0.723) 177 Comparative Example 71 1 : 2 4.55 69.2 (0.247, 0.632) 182 Comparative Example 72 1 : 3 4.60 68.3 (0.246, 0.623) 188 Comparative Example 73 3-16 : 2-53 1 : 1 4.26 75.0 (0.245, 0.655) 169 Comparative Example 74 1 : 2 4.29 74.2 (0.258, 0.613) 172 Comparative Example 75 1 : 3 4.30 73.7 (0.255, 0.694) 183 Comparative Example 76 3-16 : 2-76 1 : 1 4.33 71.3 (0.247, 0.625) 165 Comparative Example 77 1 : 2 4.41 70.5 (0.248, 0.625) 171 Comparative Example 78 1 : 3 4.45 69.3 (0.254, 0.623) 177 Comparative Example 79 3-17 : 2-62 1 : 1 5.29 57.3 (0.255, 0.693) 155 Comparative example 80 1 : 2 5.31 56.7 (0.247, 0.629) 159 Comparative Example 81 1 : 3 5.33 55.6 (0.258, 0.703) 162 Comparative Example 82 3-18 : 3-53 1 : 1 5.36 56.9 (0.247, 0.652) 128 Comparative Example 83 1 : 2 5.44 55.8 (0.246, 0.623) 135 Comparative Example 84 1 : 3 5.58 54.2 (0.247, 0.665) 144 Comparative example 85 3-19 : 2-51 1 : 1 5.63 59.1 (0.251, 0.623) 138 Comparative Example 86 1 : 2 5.71 58.3 (0.245, 0.659) 142 Comparative Example 87 1 : 3 5.77 57.6 (0.254, 0.623) 159 Comparative Example 88 3-20 : 2-53 1 : 1 5.13 55.7 (0.248, 0.651) 129 Comparative Example 89 1 : 2 5.26 54.3 (0.244, 0.654) 137 Comparative example 90 1 : 3 5.31 53.8 (0.257, 0.693) 140 Comparative Example 91 3-21 : 2-51 1 : 1 5.66 50.3 (0.248, 0.657) 133 Comparative Example 92 1 : 2 5.71 49.5 (0.253, 0.667) 146 Comparative example 93 1 : 3 5.83 48.7 (0.266, 0.655) 150 Comparative example 94 3-22 : 2-56 1 : 1 5.72 49.5 (0.257, 0.638) 126 Comparative example 95 1 : 2 5.83 48.7 (0.257, 0.633) 132 Comparative example 96 1 : 3 5.91 47.6 (0.251, 0.673) 139 Comparative Example 97 3-23 : 2-68 1 : 1 5.50 48.3 (0.255, 0.724) 122 Comparative example 98 1 : 2 5.63 47.6 (0.249, 0.662) 139 Comparative Example 99 1 : 3 5.71 47.2 (0.257, 0.633) 143 Comparative example 100 3-23 : 2-53 1 : 1 5.63 46.5 (0.268, 0.617) 118 Comparative Example 101 1 : 2 5.68 45.2 (0.252, 0.622) 120 Comparative Example 102 1 : 3 5.77 44.8 (0.252, 0.613) 123 Comparative Example 103 3-24 : 2-60 1 : 1 5.46 49.7 (0.255, 0.622) 139 Comparative Example 104 1 : 2 5.53 48.3 (0.258, 0.734) 143 Comparative Example 105 1 : 3 5.59 47.6 (0.241, 0.625) 147 Example 57 1-1 : 2-51 1 : 1 2.13 145.3 (0.251, 0.723) 487 Example 58 1 : 2 2.23 144.3 (0.247, 0.645) 491 Example 59 1 : 3 2.31 143.1 (0.263, 0.625) 499 Example 60 1 : 4 2.44 140.6 (0.258, 0.637) 501 Example 61 1 : 5 2.53 138.2 (0.262, 0.635) 503 Example 62 1-1 : 2-75 1 : 1 2.42 140.3 (0.257, 0.624) 473 Example 63 1 : 2 2.45 139.8 (0.255, 0.657) 482 Example 64 1 : 3 2.53 138.4 (0.256, 0.645) 489 Example 65 1-2 : 2-51 1 : 1 2.37 138.8 (0.255, 0.674) 453 Example 66 1 : 2 2.44 137.2 (0.244, 0.656) 469 Example 67 1 : 3 2.53 136.4 (0.257, 0.633) 477 Example 68 1 : 4 2.66 133.2 (0.268, 0.651) 478 Example 69 1 : 5 2.71 130.1 (0.243, 0.657) 480 Example 70 1-3 : 2-56 1 : 1 2.33 140.6 (0.268, 0.625) 477 Example 71 1 : 2 2.41 139.7 (0.257, 0.628) 483 Example 72 1 : 3 2.43 138.2 (0.256, 0.723) 492 Example 73 1 : 4 2.56 132.6 (0.244, 0.637) 495 Example 74 1 : 5 2.57 130.2 (0.256, 0.658) 497 Example 75 1-3 : 2-77 1 : 1 2.13 133.2 (0.243, 0.652) 413 Example 76 1 : 2 2.25 132.7 (0.267, 0.669) 429 Example 77 1 : 3 2.37 131.4 (0.259, 0.627) 440 Example 78 1-4 : 2-68 1 : 1 2.33 142.5 (0.248, 0.654) 423 Example 79 1 : 2 2.42 141.3 (0.241, 0.654) 438 instance 80 1 : 3 2.53 140.2 (0.274, 0.658) 446 Example 81 1 : 4 2.66 137.2 (0.267, 0.623) 448 Example 82 1 : 5 2.70 136.6 (0.251, 0.656) 449 Example 83 1-7 : 2-62 1 : 1 2.41 143.7 (0.263, 0.623) 406 Example 84 1 : 2 2.53 142.5 (0.254, 0.673) 413 Example 85 1 : 3 2.64 141.8 (0.245, 0.647) 432 Example 86 1 : 4 2.65 138.5 (0.264, 0.658) 435 Example 87 1 : 5 2.68 137.2 (0.267, 0.625) 439 Example 88 1-10 : 2-56 1 : 1 2.78 138.7 (0.245, 0.623) 419 Example 89 1 : 2 2.83 137.5 (0.257, 0.657) 428 Example 90 1 : 3 2.88 136.4 (0.258, 0.622) 436 Example 91 1 : 4 2.92 133.4 (0.265, 0.623) 438 Example 92 1 : 5 2.95 132.8 (0.253, 0.656) 440 Example 93 1-10 : 2-77 1 : 1 2.63 138.8 (0.258, 0.714) 400 Example 94 1 : 2 2.69 137.1 (0.244, 0.627) 405 Example 95 1 : 3 2.71 136.0 (0.269, 0.613) 411 Example 96 1-13 : 2-60 1 : 1 2.16 135.7 (0.250, 0.653) 436 Example 97 1 : 2 2.23 134.1 (0.242, 0.667) 448 Example 98 1 : 3 2.28 133.9 (0.258, 0.632) 456 Example 99 1 : 4 2.30 130.8 (0.236, 0.621) 458 instance 100 1 : 5 2.31 130.1 (0.245, 0.622) 461 Example 101 1-19 : 2-60 1 : 1 2.26 138.6 (0.254, 0.646) 463 Example 102 1 : 2 2.38 137.1 (0.256, 0.634) 471 Example 103 1 : 3 2.48 135.5 (0.253, 0.641) 483 Example 104 1 : 4 2.55 132.6 (0.253, 0.652) 485 Example 105 1 : 5 2.57 130.7 (0.247, 0.665) 488 Example 106 1-22 : 2-62 1 : 1 2.13 141.2 (0.258, 0.673) 429 Example 107 1 : 2 2.28 140.3 (0.235, 0.645) 433 Example 108 1 : 3 2.36 138.9 (0.237, 0.624) 448 Example 109 1 : 4 2.38 135.2 (0.255, 0.622) 450 Example 110 1 : 5 2.40 134.7 (0.257, 0.642) 451 Example 111 1-31 : 2-60 1 : 1 2.43 142.6 (0.244, 0.603) 403 Example 112 1 : 2 2.46 141.0 (0.253, 0.620) 419 Example 113 1 : 3 2.55 138.1 (0.255, 0.613) 432 Example 114 1 : 4 2.56 135.6 (0.256, 0.625) 435 Example 115 1 : 5 2.58 132.7 (0.257, 0.647) 436 Example 116 1-37 : 2-53 1 : 1 2.16 143.5 (0.242, 0.624) 422 Example 117 1 : 2 2.28 141.8 (0.267, 0.734) 439 Example 118 1 : 3 2.33 140.7 (0.253, 0.627) 442 Example 119 1 : 4 2.40 138.2 (0.265, 0.623) 445 Example 120 1 : 5 2.42 137.9 (0.258, 0.627) 447 Example 121 1-37 : 2-76 1 : 1 2.38 139.5 (0.256, 0.659) 419 Example 122 1 : 2 2.41 138.2 (0.275, 0.666) 426 Example 123 1 : 3 2.48 137.1 (0.266, 0.628) 438 Example 124 1-40 : 2-33 1 : 1 2.22 143.2 (0.255, 0.625) 416 Example 125 1 : 2 2.31 142.8 (0.258, 0.617) 428 Example 126 1 : 3 2.48 141.3 (0.257, 0.623) 433 Example 127 1 : 4 2.50 138.7 (0.268, 0.627) 435 Example 128 1 : 5 2.51 137.2 (0.256, 0.657) 436 Example 129 1-44 : 2-60 1 : 1 2.38 145.5 (0.247, 0.625) 423 Example 130 1 : 2 2.43 143.2 (0.265, 0.724) 442 Example 131 1 : 3 2.49 142.1 (0.255, 0.623) 453 Example 132 1 : 4 2.50 140.6 (0.254, 0.663) 455 Example 133 1 : 5 2.52 138.7 (0.265, 0.650) 456 Example 134 1-53 : 2-68 1 : 1 2.56 144.5 (0.685, 0.652) 429 Example 135 1 : 2 2.63 143.2 (0.257, 0.673) 433 Example 136 1 : 3 2.73 142.3 (0.269, 0.651) 442 Example 137 1 : 4 2.74 140.2 (0.256, 0.623) 445 Example 138 1 : 5 2.77 138.3 (0.257, 0.663) 446 Example 139 1-57 : 2-50 1 : 1 2.46 138.5 (0.286, 0.674) 468 Example 140 1 : 2 2.53 137.4 (0.271, 0.675) 479 Example 141 1 : 3 2.63 135.5 (0.274, 0.673) 481 Example 142 1 : 4 2.66 130.3 (0.267, 0.663) 483 Example 143 1 : 5 2.67 130.0 (0.286, 0.654) 484 Example 144 1-57 : 2-78 1 : 1 2.80 142.2 (0.266, 0.671) 446 Example 145 1 : 2 2.83 141.3 (0.263, 0.655) 453 Example 146 1 : 3 2.91 140.9 (0.258, 0.665) 462 Example 147 1-63 : 2-56 1 : 1 2.34 143.7 (0.273, 0.672) 477 Example 148 1 : 2 2.49 141.9 (0.270, 0.676) 483 Example 149 1 : 3 2.53 140.2 (0.286, 0.674) 498 Instance 150 1 : 4 2.55 138.1 (0.257, 0.624) 500 Example 151 1 : 5 2.56 137.6 (0.254, 0.628) 503 Example 152 1-63 : 2-77 1 : 1 2.61 137.6 (0.255, 0.633) 423 Example 153 1 : 2 2.68 136.4 (0.256, 0.683) 436 Example 154 1 : 3 2.72 135.2 (0.235, 0.644) 449 Example 155 1-71 : 2-51 1 : 1 2.41 133.9 (0.235, 0.654) 478 Example 156 1 : 2 2.53 132.1 (0.245, 0.639) 483 Example 157 1 : 3 2.68 131.7 (0.258, 0.614) 491 Example 158 1 : 4 2.70 128.6 (0.256, 0.624) 493 Example 159 1 : 5 2.71 128.3 (0.255, 0.630) 499 Instance 160 1-71 : 2-75 1 : 1 2.33 130.3 (0.253, 0.713) 453 Example 161 1 : 2 2.47 128.7 (0.247, 0.623) 462 Example 162 1 : 3 2.53 124.5 (0.258, 0.629) 473 Example 163 1-80 : 2-53 1 : 1 2.06 133.9 (0.254, 0.624) 438 Instance 164 1 : 2 2.18 132.1 (0.244, 0.624) 442 Example 165 1 : 3 2.23 131.7 (0.268, 0.623) 456 Example 166 1 : 4 2.35 129.3 (0.245, 0.641) 457 Example 167 1 : 5 2.36 128.7 (0.234, 0.653) 459 Example 168 1-83 : 2-60 1 : 1 2.11 144.9 (0.259, 0.623) 426 Example 169 1 : 2 2.23 143.1 (0.645, 0.648) 438 Instance 170 1 : 3 2.38 142.2 (0.253, 0.683) 447 Example 171 1 : 4 2.40 140.5 (0.254, 0.624) 449 Example 172 1 : 5 2.42 139.8 (0.252, 0.623) 450 Example 173 1-87 : 2-60 1 : 1 2.26 145.0 (0.269, 0.659) 453 Example 174 1 : 2 2.37 144.6 (0.289, 0.674) 462 Example 175 1 : 3 2.44 142.8 (0.251, 0.675) 478 Example 176 1 : 4 2.45 140.6 (0.264, 0.624) 479 Example 177 1 : 5 2.47 139.9 (0.252, 0.627) 483 Example 178 1-93 : 2-62 1 : 1 2.39 140.9 (0.264, 0.675) 468 Example 179 1 : 2 2.41 138.7 (0.268, 0.657) 473 Instance 180 1 : 3 2.46 136.1 (0.265, 0.643) 482 Example 181 1 : 4 2.47 135.5 (0.253, 0.676) 485 Example 182 1 : 5 2.49 135.2 (0.264, 0.623) 488 Example 183 1-94 : 2-53 1 : 1 2.33 133.8 (0.258, 0.645) 458 Example 184 1 : 2 2.49 132.5 (0.253, 0.661) 462 Example 185 1 : 3 2.57 131.1 (0.257, 0.688) 474 Example 186 1 : 4 2.58 130.6 (0.264, 0.643) 475 Example 187 1 : 5 2.60 129.3 (0.259, 0.676) 477 Example 188 1-94 : 2-76 1 : 1 2.13 132.4 (0.253, 0.627) 413 Example 189 1 : 2 2.28 130.8 (0.235, 0.618) 426 Example 190 1 : 3 2.33 129.1 (0.247, 0.623) 438 Example 191 1-95 : 2-56 1 : 1 2.26 136.5 (0.258, 0.639) 469 Example 192 1 : 2 2.37 134.8 (0.253, 0.733) 472 Example 193 1 : 3 2.43 133.2 (0.243, 0.629) 483 Example 194 1 : 4 2.44 130.3 (0.255, 0.627) 485 Example 195 1 : 5 2.48 129.7 (0.235, 0.628) 488 Example 196 1-95 : 2-77 1 : 1 2.36 136.5 (0.263, 0.634) 423 Example 197 1 : 2 2.41 135.1 (0.255, 0.625) 436 Example 198 1 : 3 2.59 134.8 (0.254, 0.669) 442 Example 199 1-99 : 2-33 1 : 1 2.46 139.5 (0.277, 0.686) 436 Instance 200 1 : 2 2.53 138.4 (0.264, 0.624) 448 instance 201 1 : 3 2.61 137.1 (0.254, 0.623) 453 instance 202 1 : 4 2.66 135.7 (0.258, 0.659) 455 Example 203 1 : 5 2.73 132.6 (0.274, 0.689) 459 instance 204 1-103 : 2-51 1 : 1 2.37 135.9 (0.257, 0.625) 432 instance 205 1 : 2 2.41 134.1 (0.243, 0.635) 444 Instance 206 1 : 3 2.53 133.6 (0.247, 0.627) 459 Instance 207 1 : 4 2.55 132.8 (0.255, 0.667) 460 Instance 208 1 : 5 2.59 132.1 (0.273, 0.684) 462 Example 209 1-105 : 2-60 1 : 1 2.08 143.2 (0.655, 0.254) 413 Example 210 1 : 2 2.13 141.5 (0.579, 0.358) 426 Example 211 1 : 3 2.29 140.6 (0.612, 0.376) 438 Example 212 1 : 4 2.30 139.6 (0.650, 0.256) 440 Example 213 1 : 5 2.33 138.8 (0.578, 0.354) 442 Instance 214 1-107 : 2-62 1 : 1 2.13 144.7 (0.255, 0.677) 435 instance 215 1 : 2 2.23 143.1 (0.266, 0.653) 449 Instance 216 1 : 3 2.34 141.8 (0.265, 0.739) 451 Instance 217 1 : 4 4.36 140.6 (0.576, 0.354) 453 Example 218 1 : 5 4.38 139.2 (0.255, 0.673) 455 Example 219 1-112 : 2-50 1 : 1 3.12 132.5 (0.257, 0.654) 387 instance 220 1 : 2 3.26 131.7 (0.683, 0.643) 392 Example 221 1 : 3 3.37 130.5 (0.267, 0.625) 399 Example 222 1 : 4 3.44 129.6 (0.243, 0.624) 401 Example 223 1 : 5 3.46 129.2 (0.264, 0.708) 403 Example 224 1-112 : 2-76 1 : 1 3.23 130.8 (0.267, 0.624) 354 Example 225 1 : 2 3.31 129.7 (0.276, 0.613) 362 Example 226 1 : 3 3.35 129.1 (0.254, 0.626) 366 Example 227 1-115 : 2-60 1 : 1 3.16 126.5 (0.249, 0.628) 374 Example 228 1 : 2 3.27 125.3 (0.266, 0.758) 382 Example 229 1 : 3 3.33 124.8 (0.253, 0.635) 388 instance 230 1 : 4 3.40 123.6 (0.275, 0.659) 390 Example 231 1 : 5 3.42 121.7 (0.261, 0.627) 391 Example 232 1-121 : 2-62 1 : 1 3.11 131.6 (0.642, 0.645) 364 Example 233 1 : 2 3.23 130.4 (0.256, 0.674) 372 Instance 234 1 : 3 3.34 128.6 (0.268, 0.666) 384 Example 235 1 : 4 3.40 128.3 (0.263, 0.627) 388 Instance 236 1 : 5 3.42 127.7 (0.642, 0.644) 391 Instance 237 1-130 : 2-56 1 : 1 3.26 133.5 (0.281, 0.674) 355 Instance 238 1 : 2 3.31 132.7 (0.274, 0.645) 361 Example 239 1 : 3 3.33 131.2 (0.267, 0.677) 369 instance 240 1 : 4 3.39 130.6 (0.644, 0.647) 371 Example 241 1 : 5 3.40 129.7 (0.273, 0.670) 373 instance 242 1-142 : 2-68 1 : 1 3.29 134.5 (0.268, 0.657) 374 Example 243 1 : 2 3.35 133.7 (0.265, 0.644) 382 instance 244 1 : 3 3.39 132.5 (0.259, 0.647) 388 Instance 245 1 : 4 3.41 132.0 (0.254, 0.675) 390 Instance 246 1 : 5 3.44 131.9 (0.257, 0.644) 392 Instance 247 1-145 : 2-60 1 : 1 2.63 128.6 (0.245, 0.645) 365 Instance 248 1 : 2 2.71 127.1 (0.274, 0.659) 371 Example 249 1 : 3 2.77 126.5 (0.261, 0.623) 378 Instance 250 1 : 4 2.79 125.7 (0.256, 0.645) 380 Example 251 1 : 5 2.80 125.5 (0.253, 0.665) 383 Example 252 1-145 : 2-77 1 : 1 2.51 123.4 (0.253, 0.675) 360 Example 253 1 : 2 2.55 122.8 (0.247, 0.644) 362 Instance 254 1 : 3 2.69 121.6 (0.248, 0.612) 366 Instance 255 1-156 : 2-62 1 : 1 2.63 130.8 (0.257, 0.654) 379 Instance 256 1 : 2 2.71 129.4 (0.258, 0.612) 382 Instance 257 1 : 3 2.83 128.7 (0.256, 0.675) 390 Instance 258 1 : 4 2.88 127.3 (0.255, 0.674) 393 Example 259 1 : 5 2.91 125.6 (0.246, 0.643) 395 instance 260 1-164 : 2-56 1 : 1 2.70 127.4 (0.259, 0.663) 387 Example 261 1 : 2 2.76 126.2 (0.256, 0.684) 392 Instance 262 1 : 3 2.83 125.5 (0.263, 0.648) 400 Instance 263 1 : 4 2.84 124.9 (0.243, 0.621) 402 Instance 264 1 : 5 2.86 124.1 (0.255, 0.623) 404 Instance 265 1-172 : 2-56 1 : 1 3.12 131.7 (0.264, 0.625) 366 Instance 266 1 : 2 3.26 130.5 (0.245, 0.623) 372 Instance 267 1 : 3 3.37 129.4 (0.255, 0.624) 383 Instance 268 1 : 4 3.39 128.2 (0.259, 0.675) 388 Instance 269 1 : 5 3.41 127.7 (0.243, 0.647) 390 Instance 270 1-172 : 2-77 1 : 1 3.28 132.4 (0.262, 0.721) 361 Example 271 1 : 2 3.33 131.2 (0.245, 0.628) 366 Instance 272 1 : 3 3.41 130.8 (0.248, 0.623) 372 Instance 273 1-176 : 2-62 1 : 1 3.36 134.7 (0.264, 0.693) 384 Instance 274 1 : 2 3.44 133.5 (0.253, 0.629) 388 Instance 275 1 : 3 3.52 132.4 (0.685, 0.623) 394 Instance 276 1 : 4 3.55 131.6 (0.258, 0.675) 395 Instance 277 1 : 5 3.56 130.7 (0.243, 0.645) 399 Instance 278 1-187 : 2-56 1 : 1 3.28 135.6 (0.264, 0.665) 370 Instance 279 1 : 2 3.37 134.2 (0.269, 0.645) 382 Instance 280 1 : 3 3.42 133.8 (0.284, 0.669) 393 Example 281 1 : 4 3.44 133.7 (0.256, 0.675) 399 Instance 282 1 : 5 3.46 132.6 (0.243, 0.643) 402 Example 283 1-200 : 2-62 1 : 1 2.89 132.4 (0.273, 0.661) 364 Instance 284 1 : 2 2.93 131.6 (0.248, 0.623) 378 Instance 285 1 : 3 3.05 130.7 (0.645, 0.658) 385 Instance 286 1 : 4 3.11 129.6 (0.267, 0.691) 388 Instance 287 1 : 5 3.13 128.8 (0.258, 0.624) 390 Instance 288 1-203 : 2-53 1 : 1 2.77 135.4 (0.257, 0.675) 372 Instance 289 1 : 2 2.83 134.6 (0.259, 0.657) 384 Instance 290 1 : 3 2.95 133.7 (0.284, 0.674) 390 Example 291 1 : 4 2.99 133.1 (0.255, 0.653) 393 Example 292 1 : 5 3.01 132.6 (0.257, 0.647) 395 Example 293 1-203 : 2-76 1 : 1 2.63 126.5 (0.273, 0.671) 362 Instance 294 1 : 2 2.75 125.4 (0.265, 0.674) 366 Example 295 1 : 3 2.84 124.6 (0.258, 0.663) 374 Instance 296 1-212 : 2-56 1 : 1 2.13 133.9 (0.256, 0.653) 387 Instance 297 1 : 2 2.26 132.7 (0.257, 0.645) 394 Instance 298 1 : 3 2.39 131.8 (0.235, 0.618) 400 Example 299 1 : 4 3.41 130.6 (0.266, 0.674) 402 Instance 300 1 : 5 3.44 130.0 (0.254, 0.653) 404 instance 301 1-212 : 2-77 1 : 1 2.63 126.8 (0.247, 0.653) 354 instance 302 1 : 2 2.66 125.4 (0.257, 0.675) 366 instance 303 1 : 3 2.71 124.1 (0.257, 0.724) 378 instance 304 1-216 : 2-50 1 : 1 3.56 115.0 (0.243, 0.639) 342 instance 305 1 : 2 3.64 113.2 (0.263, 0.436) 350 Instance 306 1 : 3 3.69 110.9 (0.255, 0.625) 355 Instance 307 1 : 4 3.71 110.5 (0.276, 0.651) 357 Instance 308 1 : 5 3.73 109.7 (0.264, 0.624) 359 Instance 309 1-216 : 2-75 1 : 1 3.62 113.6 (0.255, 0.669) 326 instance 310 1 : 2 3.74 112.0 (0.245, 0.651) 337 Example 311 1 : 3 3.82 110.7 (0.247, 0.667) 349 instance 312 1-236 : 2-56 1 : 1 3.77 112.5 (0.277, 0.652) 348 Instance 313 1 : 2 3.80 111.4 (0.265, 0.623) 352 Instance 314 1 : 3 3.83 110.9 (0.254, 0.678) 369 instance 315 1 : 4 3.85 109.7 (0.265, 0.652) 371 Instance 316 1 : 5 3.88 108.8 (0.246, 0.657) 377 Instance 317 1-259 : 2-60 1 : 1 3.55 96.4 (0.245, 0.634) 318 Instance 318 1 : 2 3.64 95.1 (0.241, 0.627) 332 Instance 319 1 : 3 3.76 94.7 (0.256, 0.654) 340 instance 320 1 : 4 3.79 94.2 (0.261, 0.653) 342 Example 321 1 : 5 3.81 93.8 (0.257, 0.661) 344 Example 322 1-272 : 2-51 1 : 1 3.62 98.4 (0.263, 0.625) 302 Instance 323 1 : 2 3.74 97.2 (0.263, 0.704) 318 Instance 324 1 : 3 3.88 96.1 (0.273, 0.669) 326 Instance 325 1 : 4 3.91 93.2 (0.262, 0.674) 328 Instance 326 1 : 5 3.94 92.6 (0.259, 0.651) 332 Instance 327 1-285 : 2-62 1 : 1 3.69 100.4 (0.268, 0.625) 329 Instance 328 1 : 2 3.70 98.7 (0.254, 0.678) 341 Example 329 1 : 3 3.78 97.0 (0.245, 0.646) 356 instance 330 1 : 4 3.82 94.5 (0.257, 0.674) 352 Example 331 1 : 5 3.86 94.1 (0.255, 0.675) 350 Example 332 1-311 : 2-62 1 : 1 3.77 105.4 (0.676, 0.629) 321 Example 333 1 : 2 3.84 103.2 (0.660, 0.618) 339 instance 334 1 : 3 3.89 99.4 (0.559, 0.568) 348 Example 335 1 : 4 3.90 98.3 (0.257, 0.664) 346 Instance 336 1 : 5 3.95 97.6 (0.249, 0.648) 344 Instance 337 1-325 : 2-53 1 : 1 1.89 155.0 (0.268, 0.654) 587 Instance 338 1 : 2 1.93 154.1 (0.253, 0.675) 593 Example 339 1 : 3 2.05 152.5 (0.254, 0.685) 600 instance 340 1 : 4 2.13 153.2 (0.256, 0.663) 603 Instance 341 1 : 5 2.19 153.9 (0.245, 0.646) 606 instance 342 1-327 : 2-51 1 : 1 1.79 150.4 (0.248, 0.651) 574 Instance 343 1 : 2 1.83 149.3 (0.243, 0.654) 583 instance 344 1 : 3 1.98 146.8 (0.277, 0.641) 591 instance 345 1 : 4 2.03 145.3 (0.265, 0.644) 593 Instance 346 1 : 5 2.12 144.1 (0.243, 0.651) 599 Instance 347 1-332 : 2-62 1 : 1 2.03 152.6 (0.268, 0.635) 532 Instance 348 1 : 2 2.16 150.7 (0.258, 0.667) 544 Example 349 1 : 3 2.27 149.4 (0.243, 0.645) 559 Instance 350 1 : 4 2.34 146.3 (0.253, 0.648) 563 instance 351 1 : 5 2.49 144.2 (0.269, 0.623) 569 Instance 352 1-334 : 2-53 1 : 1 1.98 152.6 (0.249, 0.627) 562 Instance 353 1 : 2 2.07 150.3 (0.256, 0.644) 577 instance 354 1 : 3 2.16 149.4 (0.261, 0.627) 583 instance 355 1 : 4 2.23 143.2 (0.256, 0.664) 588 Instance 356 1 : 5 2.34 140.6 (0.247, 0.658) 590 Instance 357 1-337 : 2-62 1 : 1 2.13 146.7 (0.259, 0.714) 489 Instance 358 1 : 2 2.25 145.1 (0.261, 0.649) 492 Instance 359 1 : 3 2.36 143.6 (0.267, 0.635) 507 Instance 360 1 : 4 2.41 142.7 (0.272, 0.641) 513 Instance 361 1 : 5 2.44 140.3 (0.268, 0.643) 522 Instance 362 1-339 : 2-68 1 : 1 2.03 149.5 (0.265, 0.623) 513 Instance 363 1 : 2 2.23 147.3 (0.264, 0.655) 528 instance 364 1 : 3 2.39 146.2 (0.243, 0.643) 534 instance 365 1 : 4 2.41 145.3 (0.265, 0.675) 539 Instance 366 1 : 5 2.44 144.0 (0.259, 0.657) 542 Instance 367 1-341 : 2-53 1 : 1 2.32 152.6 (0.241, 0.658) 562 Instance 368 1 : 2 2.49 151.2 (0.253, 0.625) 571 Instance 369 1 : 3 2.55 149.5 (0.258, 0.651) 588 instance 370 1 : 4 2.57 148.3 (0.268, 0.655) 591 Instance 371 1 : 5 2.59 147.7 (0.253, 0.645) 594 Instance 372 1-351 : 2-51 1 : 1 2.18 152.6 (0.256, 0.674) 567 Instance 373 1 : 2 2.26 150.0 (0.258, 0.663) 579 Instance 374 1 : 3 2.39 148.4 (0.275, 0.671) 593 Instance 375 1 : 4 2.41 147.6 (0.257, 0.658) 595 Instance 376 1 : 5 2.44 146.6 (0.243, 0.651) 598 Instance 377 1-351 : 2-75 1 : 1 2.32 146.2 (0.264, 0.675) 531 Instance 378 1 : 2 2.41 144.6 (0.257, 0.665) 548 Instance 379 1 : 3 2.44 142.7 (0.256, 0.653) 563

When comparing the results in Table 16 with those in Table 15, it can be confirmed that when the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 are simultaneously used as the main body of the light-emitting layer, the service life is improved by about 3 times, and the driving voltage and luminous efficiency Respectively improve about 40% and about 50%.

In contrast, it can be seen that when a compound not included in the scope of the present invention is used in combination with the compound of Chemical Formula 2, the service life is similar to that when the heterocyclic compound of the present invention is used alone, and the performance in driving voltage and luminous efficiency is reduced .

That is, it can be confirmed that when the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 of the present invention are simultaneously used as the host of the light emitting layer, the driving voltage, luminous efficiency, and service life are obviously excellent.

Specifically, when comparing an example in which the same heterocyclic compound of Chemical Formula 1 is used and the compound of Chemical Formula 2 has the same structure but differs only in whether the compound is substituted with deuterium, it can be confirmed that when the compound of Chemical Formula 2 substituted with deuterium is used When , the light emitting element is excellent in driving voltage, luminous efficiency, and service life.

This is because the case where the compound of Chemical Formula 2 contains deuterium is even more effective in improving the performance of the organic light-emitting device because the stability and thermal stability of the molecule are enhanced in both the compound of Chemical Formula 2 and the heterocyclic compound of Chemical Formula 1.

In addition, in the case of combining the elements of Chemical Formula 1 and Chemical Formula 2, especially when the combination ratio of the N-type host and the P-type host is 1:3, the best driving, efficiency, and service life results are exhibited. The result is an increase in drive and service life and a decrease in efficiency as the proportion of N-type hosts decreases. Specifically, when the ratio of N-type hosts is less than 23%, ie, a ratio of 1:4, the driving and service life tend to be similar or gradually increase. In contrast, it can be confirmed experimentally that the efficiency tends to decrease drastically. Therefore, especially when a device is formed by combining the compound of the present invention, when the ratio of the N-type host is 30% or more, good results in terms of driving, efficiency, and service life can be obtained. Thus, it can be confirmed that Chemical Formula 1 plays an important role in increasing the efficiency of the device.

< Experimental Example 3> - HOMO/LUMO/SOMO In the case of the material of Compound 1-1 of the present invention, as can be confirmed in Table 17, when observing the electron cloud distribution in the HOMO and LUMO states, LUMO is distributed in three in the oxazine moiety and the HOMO is distributed in the heterocycle moiety. In organic compound molecules, holes move through HOMOs and electrons move through LUMOs. Deuterium-substituted moieties have a higher packing density than hydrogen-substituted moieties. Therefore, in the deuterium-substituted part, the distance between molecules is closer, making the hole or electron move faster, and in the present invention, the hole characteristics are enhanced by replacing the HOMO part of the transport hole with deuterium.

It can be confirmed that when compound 1-1, which has a molecular hole characteristic enhancement effect, and a novel dopant with enhanced efficiency characteristics are used to make an OLED device, compared with Comparative Example 3-17, the recombination zone (RZ) is located in the light-emitting layer center, and thereby improve efficiency and service life.

In addition, when the triazine responsible for LUMO is substituted with deuterium as in Comparative Example 3-21, electrons move faster, making the recombination zone (RZ) more biased towards HTL side.

Consequently, both efficiency and service life are reduced as a result. When the entire compound was substituted with deuterium as in Comparative Example 3-1, both electrons and holes became faster, and thus RZ was unchanged, showing an efficiency level similar to that of Comparative Example 3-17. In other words, it could be confirmed that when the heterocyclic compound of Chemical Formula 1 of the present invention is used as the host of the light emitting layer, the light emitting efficiency and the service life are obviously excellent.

For reference purposes, the radical cation single-occupied molecular orbital (SOMO) distribution of compound 1-1 can be identified in Table 17 below. When the SOMO moiety is substituted with deuterium, the number of neutrons in the nucleus increases compared to when the SOMO moiety is substituted with hydrogen, making it possible to improve the stability of radical cations that can occur when driving the element. Therefore, when Chemical Formula 1 of the present invention is used as the host of the light emitting layer, the stability of molecules during driving of the element is excellent. [Table 17] HOMO electron distribution LUMO electron distribution SOMO electron distribution

< Experimental Example 4> —Confirmation of Recombination Zone A recombination zone (RZ) confirmation experiment was performed by the same method of manufacturing an organic light-emitting element as in Experimental Example 1. The difference from Experimental Example 1 lies in the doping position of the green phosphorescence in the light-emitting layer.

In #1 of FIG. 4, the entire light-emitting layer was doped with a green phosphorescent dopant, and the doped light-emitting layer was used as a comparison group. In case of #2, only 120 angstroms of the colored part (near the hole transport layer) was doped, and only 240 angstroms of the body was deposited on the rest. In the case of #3, only 120 Angstroms of the colored portion (in the center of the emissive layer) was doped in the image below, and the host was deposited only on the remaining uncolored portion. In the case of #4, only 120Å of the colored part (near the hole blocking layer) is doped in the lower image, and the host is only deposited on the remaining colorless part.

In the case of Comparative Example Compound 3-1 and Comparative Example Compound 3-17, RZ is close to the hole transport layer (HTL), making #2 have the best efficiency and lifetime. The electron transfer rate of this display compound is faster than the hole transfer rate. It was confirmed that Comparative Example Compound 3-21 further increased the electron transfer rate by substituting the triazine moiety responsible for LUMO with deuterium compared to Compound 3-1 and Compound 3-17, and thereby increased the service life of #2 and further Reduce the service life of #3 and #4.

In contrast, compound 1-1 exhibited the highest efficiency and lifetime at #3 (located in the center of the emitting layer). This is because the hole transport feature is strong, the hole transfer rate is relatively fast, and the transfer of holes and electrons is well balanced as described above, confirming that the RZ is near the center of the EML layer.

The above can be confirmed by an experiment of confirming the current density with voltage by fabricating a hole-only device (HOD), and the results are shown in FIG. 5 .

In addition, FIG. 6 below shows the measurement of current density with voltage by fabricating a hole-only device (HOD) using a compound having a deuterium substitution rate different from that of Compound 1-1. In FIG. 6, it can be confirmed that the greater the deuterium substitution rate of the compound of the present invention, the faster the hole transfer rate. Throughout the experiment, it can be confirmed experimentally that when the deuterium substitution rate is 50% or greater, the compound of the present invention exhibits more balanced charge and hole transport characteristics in the device, and thus achieves the maximum efficiency and service life.

100: Substrate 200: positive electrode 300: organic material layer 301: Hole injection layer 302: Hole transport layer 303: Luminescent layer 304: Hole blocking layer 305: Electron transport layer 306: Electron injection layer 400: negative electrode

1 to 3 are views each illustratively showing a stack structure of an organic light emitting element according to an exemplary embodiment of the present specification. Figure 4 is a view obtained by experiments to confirm the recombination zone (RZ). FIG. 5 and FIG. 6 show the results of an experiment of confirming the current density according to the voltage by manufacturing a hole-only device (HOD).

100: Substrate

200: positive electrode

300: organic material layer

400: negative electrode

Claims (16)

A heterocyclic compound having the following chemical formula 1: [chemical formula 1]

In Chemical Formula 1, X is O; S; or CRR', L is a direct bond; or a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, l is an integer of 1 to 3, and When l is 2 or greater than 2, L' are the same or different from each other, A is an aromatic ring having 6 to 60 carbon atoms, which is unsubstituted or substituted with deuterium; or a heterocyclic ring having 2 to 60 carbon atoms Ring, which is unsubstituted or substituted with deuterium, R, R', Ar1 and Ar2 are each independently hydrogen; deuterium; halo; cyano; substituted or unsubstituted alkane having 1 to 60 carbon atoms substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; substituted or unsubstituted heterocycloalkyl having 2 to 60 carbon atoms; having 6 to 60 carbons Atomic substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms, H is hydrogen and D is deuterium, d is an integer from 0 to 6; and chemical formula 1

The deuterium content is greater than 0%. The heterocyclic compound as described in Claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 1-1: [Chemical Formula 1-1]

In Chemical Formula 1-1, H1 to H4 are each independently hydrogen; or deuterium, and the definitions of other substituents are the same as those in Chemical Formula 1. The heterocyclic compound as described in Claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formula 1-1-1 to Chemical Formula 1-1-6: [Chemical Formula 1-1-1]

[Chemical formula 1-1-2]

[chemical formula 1-1-3]

[chemical formula 1-1-4]

[chemical formula 1-1-5]

[chemical formula 1-1-6]

In Chemical Formula 1-1-1 to Chemical Formula 1-1-6, H1 to H12 are each independently hydrogen; or deuterium, at least one of H1 to H12 is deuterium, and the definitions of other substituents are the same as in Chemical Formula 1 Same definition. The heterocyclic compound as claimed in claim 1, wherein Ar1 and Ar2 are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a heteroaryl group having 2 to 30 carbon atoms groups, which are substituted or unsubstituted and include O or S. The heterocyclic compound as claimed in claim 1, wherein the chemical formula 1 includes the structures of the following chemical formula A and chemical formula B and optionally includes the structure of the following chemical formula C, and the deuterium content of the following chemical formula B is 50% or greater than 50% and 100% % or less than 100%: [Chemical Formula A]

[chemical formula B]

[chemical formula C]

In chemical formula A to chemical formula C, each structure

means a site of bonding to another structure, and L' is a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, and the definitions of other substituents are the same as those in Chemical Formula 1. The heterocyclic compound as claimed in item 1, wherein chemical formula 1 is represented by any one of the following compounds:

. An organic light emitting element, comprising: a first electrode; a second electrode; and an organic material layer having one or more layers disposed between the first electrode and the second electrode, Wherein one or more layers of the organic material layer include the heterocyclic compound as described in any one of claims 1 to 6. The organic light-emitting device according to claim 7, wherein the organic material layer including the heterocyclic compound further includes a compound of the following chemical formula 2: [chemical formula 2]

In Chemical Formula 2, L1 and L2 are each independently a direct bond; or a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, l1 and l2 are each an integer of 1 to 3, and when l1 and l2 are each 2 or greater than 2, the substituents in the brackets are the same or different, R1 and R2 are each independently hydrogen; deuterium; halogen; cyano; substituted or unsubstituted with 1 to 60 carbon atoms Substituted alkyl; substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; substituted or unsubstituted heterocycloalkyl having 2 to 60 carbon atoms; having 6 A substituted or unsubstituted aryl group of up to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group of 2 to 60 carbon atoms, H is hydrogen and D is deuterium, and d1 and d2 are each are independently an integer of 0 to 7. The organic light-emitting device as claimed in item 8, wherein the deuterium content in Chemical Formula 2 is 0% or 10% to 100%. The organic light-emitting element as claimed in item 8, wherein chemical formula 2 is represented by any one of the following compounds:

. The organic light-emitting element according to claim 7, wherein the organic material layer includes a light-emitting layer, and The light emitting layer includes the heterocyclic compound of Chemical Formula 1. The organic light-emitting element according to claim 8, wherein the organic material layer includes a light-emitting layer, and The light emitting layer includes the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2. The organic light-emitting device as claimed in claim 7, further comprising one or more layers selected from the group consisting of: light-emitting layer, hole injection layer, hole transport layer, electron injection layer, electron transport layer , electron blocking layer and hole blocking layer. A composition for an organic material layer of an organic light-emitting element, comprising the heterocyclic compound as described in Claim 1. The composition as described in Claim 14 further includes the compound of the following chemical formula 2: [chemical formula 2]

In Chemical Formula 2, L1 and L2 are each independently a direct bond; or a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, l1 and l2 are each an integer of 1 to 3, and when l1 and l2 are each 2 or greater than 2, the substituents in the brackets are the same or different, R1 and R2 are each independently hydrogen; deuterium; halogen; cyano; substituted or unsubstituted with 1 to 60 carbon atoms Substituted alkyl; substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; substituted or unsubstituted heterocycloalkyl having 2 to 60 carbon atoms; having 6 A substituted or unsubstituted aryl group of up to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group of 2 to 60 carbon atoms, H is hydrogen and D is deuterium, and d1 and d2 are each are independently an integer of 0 to 7. The composition according to claim 15, wherein the weight ratio of the heterocyclic compound of the chemical formula 1 to the compound of the chemical formula 2 in the composition is 1:10 to 10:1.

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